Spectroscopic and Theoretical Aspects

1
Spectroscopic and Theoretical Aspects

BY R . DEVONSHIRE
1 Introduction
The format of this report is similar to that of my last contribution. In general,
emphasis is placed on intramolecular photophysical processes. Several aspects of
photochemical excited-state decay processes are covered in later chapters of this
volume.
In the two-year period covered in this report there have been a number of
significant developments, amongst which are the following: (0 the relentless
progress of ab initio methods of calculating excited-state properties as exemplified
by calculations on a model of the active site in the iron-sulphur protein rubredoxin,
(ii) fresh impetus and progress towards methods of calculation which avoid the
Born-Oppenheimer separation, (iii)a major study of cyclic n-electron systems that
uses magnetic circular dichroism, which should advance the wider application of
this technique, (iv) the development of the concept of a proximity effect to interpret
the photophysical properties of N-heterocyclics, (v) the remarkable observations of
mode-to-mode vibrational-energy flow in the first excited singlet states of benzene
and aniline, and (vi) the probing of homogeneous linewidths in fluid solutions in
studies of the anti-Kasha fluorescence of aromatic hydrocarbons.
2 Calculations of Electronically Excited States

Methods.-The application of ab initio quantum-mechanical calculations to
problems of interest to experimental photochemists has been discussed briefly. The
effect of the choice of basis set, including the addition to the basis of so-called
‘polarization functions’, and of the extent of configuration interaction on
calculations of electronic spectra, the effect of substituents and geometry upon the
relative energies of states, and of potential surfaces for chemical reactions of excited
states are all illustrated by examples taken from the recent literature. A new
restricted self-consistent field (RSCF) method has been proposed for the calcu-
’
lation of excited states. The excited-state wavefunction obtained from RSCF
guarantees the orthogonality with the Hartree-Fock (HF) ground state and
satisfies a number of Brillouin-type theorems. Cluster expansion is a technique for
obtaining exact wavefunctions from approximate ones. When applied to open-shell
systems it takes the form of the symmetry-adapted cluster (SAC) expansion
‘ N. C. Baird, Pure Appl. Chem., 1977 49, 223.
N. Ohmichi, J . Chem. Phys., 1977, 67, 1669.
1
2 Photochemistry
method. The ground state Jlg of a given spin-space symmetry is given in equation
(l), where qg is the normalization factor, 8 the symmetry projector, C , the
coefficients obtained from variational equations, S,+ the symmetry-adapted

excitation operator, and (Do a reference wavefunction. It has been shown that the set
of functions {ak), where (Dk = r]kp8Sk+#g' (P = 1 - I t,!Igx t,!IgI), forms a basis for
the excited states of the same symmetry as the & and can lead to exact excited
states. The method can be extended to excited states having symmetries different
from the ground-state symmetry. A new method for calculating SCF wavefunctions
for the excited states of atoms and molecules has been proposed in which for every
iteration a number of diagonalizations of matrices representative of different
operators are ~ n d e r t a k e nThe
. ~ procedure results in a rapid convergence to the
correct SCF limit. The variational bounds to excited states calculated from a
generalized Brillouin-Wigner equation and from a projection operator method
have been investigated.
A much improved scheme for the calculation of multiconfiguration self-
consistent field (MCSCF) wavefunctions has been published recently. The authors
assert that their scheme is a superior one for constructing computer programs for
the MCSCF method and that it leads to programs with maximum efficiency.The
authors introduce an exponential transformation for the trial state functions in a
manner similar to an exponential spin-orbital transformation previously used in the
method and which is intended to improve the convergence properties.
A modified Rydberg formula for atomic states has been suggested that gives
accurate energies of [core] (ns2 'S) terms for a wide variety of atoms. The method '
can also be applied to [core] (nlnl' ""L) terms and extended to include
configurations of the type [core] npN ( N = 1-6). In HF calculations the core
orbitals are frequently replaced by an effective potential or pseudopotential. An
analysis of the use of pseudopotentials in local-density (LD) formalism calculations
shows that their application there may be more appropriate than in HF calculations
where more approximations are involved. * An LD pseudopotential treatment of
several excited and ionic states of first-row atoms showed errors due to the frozen
core to be less than hartree. The first-order HF equations of the ls2p3s 4P0
state of three-electron atomic systems have been solved exactly using the nuclear
charge expansion method. There is only limited experimental information
available at the present time on these doubly excited states of the lithium
isoelectronic sequence, but discrepancies have been noted between values calcu-
lated previously using a variation method and experimental assignments. The
discrepancies may arise from interactions between the near-degenerate states
ls2s3p 4P0,ls2p3s 4P0, and ls2p3d 4P0(vide infra). The problem of variational
collapse in calculations of excited states which are not the lowest of their symmetry
H. Nakatsuji, Chem. Phys. Lett., 1978, 59, 362.
R. Colle, R. Montagnani, P. Riani, and 0.Salvetti, Theor. Chim. Acta. 1978,48,257;ibid., 1978,48,251.
G . Tuchetti, F. Ortolani, and C. Sagretti, Nuovo Cimento SOC. Ztal. Fis. A , 1978, 44, 21 1 .
F. H. Read, J . Phys. B, 1977, 10, 449.
' C. C. J. Roothaan, J. Detrich, and D. G. Hopper, Int. J . Quantum Chem., 1979, 13, 93.
S. Topiol, A. Zunger, and M. A . Ratner, Chem. Phys. Lett., 1977, 49, 367.
S. R . Samanta and M. A. Ali, Int. J . Quantum Chem., 1977, 12, 561.
Spectroscopic and Theoretical Aspects 3
is central to a debate in the recent literature. In response to a paper critical of their
earlier work two authors have argued that their method for truncated Hamiltonian
matrices, which chooses the root that minimizes the energy as well as the correlation
overlap (X/X ), yields upper bounds and does not suffer variational collapse. l o
Their polemk has prompted a reply. The Galerkin-Petrov (GP) method involves
the application of the method of moments to obtaining approximate solutions to
operator equations such as the Schriidinger equation. It has been shown that with
care the GP method can be used successfully to calculate excited states of the same
symmetry classifications as the ground state.
A non-relativistic SCF method for calculating the higher excited states of atoms
has been developed, l 3 and electron correlation in the ground and excited states of
first-row atoms has been discussed.l4 The extension of the Madelung rules for the
order of the filling of successive electron shells in the ground states of neutral atoms
to excited states has been investigated. l 5 The two general rules state that (a) the
electron shells are filled in the order of increasing values of the quantum number
sum n + I, where n is the principal quantum number and 1 the azimuthal quantum
number of the shell (nl),and (b) for electron shells with the same value of n + 1( = k
in the notation of the author) the shells are filled in the order of increasing n or
decreasing 1values. These rules were found to hold exceptionally well for the levels
of the valence electron in the alkali-metal atoms and for singly ionized alkaline-
earth atoms. It is suggested that there may be a group theoretical explanation for
this k ordering. The author extended his observations to include a large number of
other ‘one-electron’ spectra and confirmed the validity of k as an ‘energy-ordering’
quantum number and of the characteristic patterns for groups with constant k.l6
Figure 1 shows the regions of validity of k ordering and hydrogenic (H) ordering.
The calculation of the excited states of closed-shell systems has been investigated
using the direct minimization SCF technique, which is based on the two-by-two
rotation of orbitals. l 7 The technique was applied to the excited states of H 2 0 and
FNO and showed, surprisingly, that the relaxation of doubly occupied orbitals, in
contrast to that of the excited-state orbital, always gives a significant contribution
to the lowering of the excited-state energy in the SCF process. This observation calls
into doubt electron-hole potential (EHP) calculations in which the relaxation of
ground-state orbitals via mixing with the virtual ones is disregarded. The EHP
method has recently been applied to problems of photochemical interest, using
various standard parameter sets (CNDO/S, INDO/S, MIND0/2), and in spite of
the observations in the paper above the results were regarded as satisfactory. A
form of the Rayleigh-Schrodinger perturbation theory has been developed which
can be applied to the calculation of low-lying excited states. In contrast to the
many-body perturbation theory (MBPT), where Slater determinants are used as the
lo C. A. Nicolaides and D. R. Beck, Phys. Rev. A , 1978, 18, 1307.
l1 W. L. Luken and 0. Sinanoglu, Phys. Rev. A , 1978, 18, 1313.
K. Jankowski, D. Rutkowska, and A. Rutkowski, Theor. Chim. Acta, 1978, 48, 119.
l3 J . Brzezowska, Acta Phys. Pol. A , 1078, 54, 243.
l4 D. R. Herrick and M. E. Kellman, Phys. Rev. A , 1978, 18, 1770.
l5 R. M. Sternheimer, Phys. Rev.A , 1977, 15, 1817.
l6 R. M. Sternheimer, Phys. Rev. A , 1977, 16, 459; ibid., 1977, 16, 1752.
l7 J. Mrozek and A. Golebiewski, Int. J . Quantum Chem., 1977, 12, 207.
la J. Sauer, Chem. Phys. Lett., 1978, 55, 119.
l9 E. R. Davidson and C. F. Bender, Chem. Phys. Lett., 1978, 59, 369.
4 Photochemistry
unperturbed states, it is able to treat corrections to a multiconfiguration function of
zero order.
t
2-N
Z
Figure 1 Regions of validity of k ordering and hydrogenic (H) ordering of the excited-state
levels of neutral atoms and ions with small degree of ionization Z-N ( Z is the atomic number, N
is the number of electrons). The curve separating the two regions is plotted as a graph of Z-N
vs. z
(Reproduced with permission from Phys. Rev. A , 1977, 16, 459)
The local approach for the calculation of electronic correlation energies in

molecules has been generalized to excited states.20The method was applied to a
system for which an exact solution was available (Hs ring) and found to give results
as good as those expected for ground-state calculations. The application of semi-
empirical LCAO-SCF-MO calculations to n-electron systems is known to have a
number of shortcomings. These probably arise from differences in the E-n
interactions in singlet and triplet states and from electron correlation effects. The
X-ll interactions have been included explicitly in a derivation of the effective IT-
electron Hamiltonian for excited states of n-electron systems. 2 1 In calculations of
n-fl excitation energies using this Hamiltonian the PPP method is used for the
ground state. Then the effective electron-repulsion integrals are evaluated, and
finally a singly excited configuration interaction method (SECI) is used, in which
o-dc and ~l-+ configurations interact through exchange-type MO integrals over 71-
and a-MOs. In a later paper the authors consider the effect of the X-rI interaction
on the oscillator strengths of n-fl transitions in benzene and naphthalene
derivatives. An all-valence LCAO-MO-SCF-INDO method has been applied
successfully to the calculation of electronic transition energies and (3thermolecular
properties,23and a recent observation that equations (2) and (3) (where Emolecule is
*O P. Horsch, 2. Phys. B, 1979, 33, 43.

21 I. Maki, K. Kitaura, and K. Nishimoto, BUN. Chem. SOC.Jpn., 1977, 50, 1720.
22 I. Maki, K. Kitaura, and K. Nishimoto, Bufl. Chem. SOC. Jpn., 1978, 51, 401.
23 J . Lipinski, A. Nowek, and H. Chojnacki, Actu Phys. Pol. A , 1978, 53, 229
the total energy of the molecule and V,, and V,, are the nuclear-electronic and
-
nuclear-nuclear interaction energies, respectively) accurately ( 1 Oh) hold for the
ground states of a large group of neutral molecules has been extended to consider
excited and ionic states, where they were found to be just as accurate
approximations. 24
Results.-No attempt has been made to report on the extensive literature on atomic
systems, and this has made it possible to increase coverage of the results of
calculations on molecular systems.
An interesting feature of the electronic spectroscopy of molecular hydrogen is
that the lowest '&' excited state is characterized by a double-minimum
internuclear potential. Accurate calculations of this potential have previously given
satisfactory agreement with the experimental vibrational-rotational spectra of this
'
E,F Eg' state. Following the original observation of this double-minimum
potential it was predicted that the next three 1%' excited states would behave
similarly. A recent calculation of the Born-Oppenheimer potential of the second
excited 'q' state, designated G,K 'q', has found such minima,25 and the
potential has subsequently been used to calculate its vibrational levels.2 6 There is
poor agreement with the experimentally observed vibrations of the G and K states,
indicating the necessity of adiabatic corrections to the potential. These double
minima can also be seen in the results of ab initio calculations of the potential curves
and wave functions of a number of excited states of H,.,' The calculations are
based on the demi-H,' model for Rydberg states and include a complete
configuration interaction (CI) calculation. The double minima are discussed in
terms of the occupation numbers of the natural spin orbitals. Interestingly, the
curves of the occupation numbers with respect to internuclear distance display a
non-crossing rule in analogy to that for potential curves. The van der Waals region
(5-10 ao)of the lowest excited state of H,, b3Z,,', has been investigated using the
modulated form of the second-order Murrell-Shaw-Musher-Amos (MS-MA)
perturbation theory. 2 8 It is concluded that the 'physical' interactions are more
difficult to calculate than those determining the chemical bond. Ab initio calcula-
tions, using a small basis, have been used to investigate the Rydberg and valence-
shell characters of the low-lying B'C,' and b3C,+ states of the H, molecule.29
A recent paper has reported the measurement of an electronically excited state of
H,.,' The observed levels were attributed to vibrational levels in the upper
Jahn-Teller sheet of H,,and their energies and intensities were compared with
existing calculations.
The Born-Oppenheimer potential surfaces for the three lowest singlet electronic
states of the H, molecule with trapezoidal geometry 3 1 and for the four lowest
singlet states of the H, molecule with 'triply right' (C2Jtetrahedral geometry "
'' P. Politzer, J . Chem. Phys., 1978, 69, 491.

25 R . M. Glover and F. Weinhold, J . Chem. Phys.. 1977, 66, 303.
26 B. G. Wicke, J . Chem. Phys.. 1978, 68, 337.
27 S. Kehl, K. Helfrich, and H. Hartmann, Theor. Chim. Acta, 1977, 44, 3 5 1 .
28 V. Magnasco, G. Figari, and M. Battezzati, Chem. Phys. Lett., 1977, 50, 138.
29 T. Noro, K. Tanaka, and K . Ohno, J . Phys. Soc. Jpn., 1977, 43, 1351.
30 M. Vogler, Phys. Rev. A . 1979, 19, 1.
3L W. Gerhartz, R. D. Poshusta, and J . Michl, J . Am. Chem. Soc.. 1976, 98, 6427.
32 W. Gerhartz, R . D. Poshusta, and J. Michl, J . Am. Chem. SOC.,1977, 9!l, 4263.
6 Photochemistry
have been calculated from an ab initio valence-bond (VB) method employing a
minimum basis set (STO-4G). The particular interest of the results is their relevance
not only to aspects of the photochemistry of H, and H, and the general problem of
useful representations of six-dimensional space but also to the modelling of more
complex systems where analogous topology may be identified. To illustrate the
latter point the authors draw analogies between trapezoidal H, and a reaction in
organic photochemistry effectively between four electrons in four atomic orbitals
referred to as a 2s + 2s pericyclic reaction, and in the case of tetrahedral H,
geometry they draw attention to the propensity for diagonal bonding in the S, state
of a pericyclic array of 4N interacting atomic orbitals. This interesting theme is
continued in another paper that models organic photochemical reactions on H,
excimer states. "
The spectroscopy of the rare-gas dimers is clearly of considerable current interest
to research into ultraviolet lasers. A timely paper has presented ab initio CI
calculations of the potential curves of sixteen of the lowest excimer states of Ar,. 34
The results agree well with the limited experimental information available for these
states. Of similar interest are SCF calculations of the ground 'Zg+state of Xe,, the
first four states of the Xe 2 + ions, and eight excimer states of Xe ,. 35 The calculations
use an approach to heavy-atom calculations, in which the core electrons are
replaced with an effective potential that also includes relativistic effects. The
application of perturbation theory to the study of the electronic structure of rare-
gas halide excimers has been shown to give quantitatively similar results to previous
ab initio calculation^.^^ The electrostatic model used in the paper includes mixing
between the ionic excimer and neutral ground configurations, which proves to be
significant to the crossing of the excited Z and n curves. Of the rare-gas
monohalides only the neon monohalides have not been studied experimentally
owing to the short wavelength of the fluorescence. Following calculations of the
potential-energy curves for the lowest four states of NeF and of transition
moments, the fluorescence-emission spectrum of NeF has been predicted.37 It is
dominated by the charge-transfer band 2 l X -+ 12Z at 108nm, and the result is
shown in Figure 2. Further information of interest in the design of laser systems lies
in the results of ab initio calculations of the potential-energy curves of Ne,F.38
There is both experimental and theoretical evidence for the existence of a ,B, state
in the analogous molecule Ar,F, and it is reasonable to expect the ionic states of the
Ne,F molecule to be even more strongly bound. Calculations using a valence
double-zeta basis set and an adequate CI showed that indeed the N e + F - ' B , state
was bound by 0.76 eV relative to its lowest dissociation limit, Ne + 2,Z'NeF. Ab
,+
initio electronic potential-energy surfaces for doublet HeH 39 and comparisons
between the theory and experimental observations of the visible excimer bands of
potassium- and sodium-noble-gas molecules 40 have been published.
33
J. D. Goddard and I . G . Czizmadia, Prog. Theor. Org. Chem., 1977, 2, 370.
34 F. Spiegelmann and J . P. Malrieu, Chem. Phys. Lett., 1978, 57, 214.
35
W. C. Ermler, Y. S. Lee, K. S. Pitzer, and N. W. Winter, J . Chem. Phys., 1978, 69, 976.
36
M. Krauss, J . Chem. Phys., 1977, 67, 1712.
37
N. W. Winter, C. F. Bender, and T. N. Resagno, J . Chem. Phys., 1977,67, 3122.
'13 C. F. Bender and H. F. Schaefer, tert., Chem. Phys. Lett., 1978, 53, 27.
39
D. R . McLaughlin and D. L. Thompson, J . Chem. Phys., 1979,70, 2748.
40
A. C. Tam, T. Yabuzaki, S. M. Curry, and W. Happer, Phys. Rev. A . , 1978, 18, 196.
The so-called semiclassical/adiabatic technique has been used to calculate the
non-adiabatic-transition probabilities in systems of three adiabatic molecular states
of the same ~ y m m e t r y .Applied
~' to diatomic alkali metals the results may be used
.-
Y 1.0
C
3
0.9
4m
3 0.8
.-
w
p
c,
0.7
C
- 0.6
0.5
0.4
0.3
0.2
0.1
0.0
100 105 110 115 120
Wavelength/ nm
Figure 2 Calculated Puorescence for the 22C+ 1 'Z transition (curve a), the Z 2 l I + 1 211
transition (curve b), and the sum of the two (curve c ) rescaled to unity at its maximum
(Reproduced with permission from J . Chem. Phys., 1977, 67, 3122)
to estimate non-adiabatic effects in the photodissociation of the molecular B'q,

state and in the collisional excitation of individual atoms. Accurate calculations of
the potential curves of the nine low-lying electronic states of LiNa have been
published. 4 2 Model potentials are used whose ability to account for core-valence
correlation effects is established by the accurate calculation of the ground-state
dipole moment. In connection with the dimers of the alkali metals it is appropriate
to mention some notable experimental measurements on the NaK dimer that have
led to accurate potential-energy curves for the lowest-bound states X ' Z + and D 'II
and the repulsive triplet state 3C+.43a
Dimers of the Group I1 metals are suitable candidates for the active media of
tunable lasers. They are known to exhibit excimer-type emissions, but there is little
information available on the dimer potential-energy curves. MCSCF and CI
techniques have been used to calculate such curves for all of the states of Mg,
arising from the ' S + ' S , ' S + 3P, and ' S + 'Patomic asymptotes and for the
lowest '&,+ and 'Q, states of Mg2+.43b The authors argue that Mg, is a better
prototype of Group I1 metal dimers than Be,. The ground state of Mg, was found
41 E. A. Gordeev, E. E. Nikitin, and A. I. Shushin, Mol. Phys., 1977, 33, 161 1.

42 P. Habitz, W. H. E. Schwarz, and R. Ahlrichs, J . Chem. Phys., 1977, 66, 51 17.
43 (a) E. J. Breford and F. Engelke, Chem. Phys. Lett., 1978,53,282. (b)W. J. Stevens and M. Krauss, J .
Chem. Phys., 1977,67, 1977.
8 Photochemistry
to be essentially repulsive with a small van der Waals well (-600cm- '), and all of
the excited states of Mg,, shown in Figure 3, except for the 37ru and 'Zg+ are bound
states. Of special note is the lowest excimer state, 37rg, which as a metastable state
could be particularly important to laser systems.
I 1 1 I I I I I 1 I
' I I I I I 1 I t 1 2
4 5 6 7 8 9 10 II 12 13
R /bohr
Figure 3 Potential-energy curves.for the excited valence states of Mg,. The dashedportions of
the 'nuand 2'Zg+curves indicate regions that have not been investigated directly but are
estimated by joining known short-range and long-range behaviour
(Reproduced with permission from J . Chem. Phys., 1977, 67, 1977)
As a test of the applicability of pseudopotential techniques to calculations of

excited-state properties, the potential curves of the ground and lowest-excited states
of AlH have been c a l c ~ l a t e d . ~ ~ spectrum
The of AlH is well known, but apparently,
prior to this study, no calculations of the states in this simple molecule have been
published. The results were found to agree well with experimental measurements,
and in addition three new states were identified.
Recent photodetachment experiments have been interpreted to show a value of
',
0.845 f 0.03 eV, or 19.5kcal mol- for the To value of the transition between the
44
M . Pelissier and J. P. Malrieu, J . Chem. Phys., 1977, 67, 5963
,,
two lowest states, ,B, and 'A of meth~lene.,~ This value was considerably higher
than the previously accepted, theoretically predicted, and experimentally measured
values, which converged on a value around 0.5 eV or 1 1 kcal mol- '. A recent paper
has presented the results of ab initio calculations, using a multi-reference double-
,,
excitation (MRD) CI technique of the ' A ,B,, and ' B , states of CH, and the ,B1
and , A , states of CH,-, and these have enabled the authors to suggest a re-
interpretation of the results of the photodetachment experiment, which brings them
,
into good agreement with earlier work.46 The 'A + ,B1 To value of 1.05 eV
observed in the photodetachment experiment agreed well with calculated values. A
number of the low-lying excited states of the CH2+ion have been investigated by ab
initio GTOSCF CI method^.^' A laser-induced fluorescence study of CH,
produced in ketene photolysis resulted in a prediction of the ,B, to ' A , energy
',
difference (not To)of 8.1 & 0.8 kcal mol- which is in general agreement with the
above calculation^.^^ A general discussion of the nature of the low-lying excited
states of saturated molecules is included in a study of the ' B , ( l T , ) state of
methane.,' The character of the excited states in such molecules can rapidly change
from Rydberg to valence or vice versa with small changes in geometry. This point is
developed in a discussion of the photodissociation of methane to CH, and H,, in
which a low-lying vertical state of CH,, commonly characterized as a Rydberg
state, correlates with a low-lying valence state in the product, ' B , CH,. The study
has been extended to other features of the photochemistry of C H , using
calculations with an improved basis set.50 The vertical transition energies of the
lower excited singlet states of CH, have been calculated by a bond-orbital
method,51 and the structure and bonding in the excited states of n-alkanes,
,
C,,H2,+ (n = 1-5), have been investigated by use of the semi-empirical INDO
method with CI.', The application of minimal basis-set calculations in the latter
study is supported by previous studies of H ,O and of HCHO and C ,H , in which it
has been possible to compare ab initio calculations and experimental results,
respectively, with the results of semi-empirical calculations.
The effect of improving the valence and Rydberg parts of the basis set on the low-
lying excited states of silane has been investigated. 53 The singlet states were found
to be essentially Rydberg states, whereas the triplet states have significant valence
character. The previously effective use of the one-centre expansion (OCE) SCF MO
and improved virtual orbital (IVO) approximations in calculating the excited states
of H,O and NH,54 has been repeated for the hydrides of some second-row atoms,
H,S, PH,, and SiH,. 5 5 SCF CI and MCSCF CI ab initio calculations of the ground,
45 P. F. Zittel, G. B. Ellison, S. V. O'Neill, E. Herbst, W. C. Lineberger, and W. P. Reinhardt, J . Am.

Chem. SOC.,1976, 98, 3731.
46 S.-K. Shih, S. D. Peyerimhoff, R. J. Buenker, and M. Perk, Chem. Phys. Lett., 1978, 55, 206.
47 C. Galloy and J. C. Lorquet, Chem. Phys., 1978, 30, 169.
48 R. K. Lengel and R. N. Zare, J . Am. Chem. SOC.,1978, 100, 7495.
49 M. S. Gordon, Chem. Phys. Lett., 1977, 52, 161.
50 M. S. Gordon and J. W. Caldwell, Jerusalem Symp. Quantum Chem. Biochem., 1977, 10, 257.
51 S. Katagiri and S. Kohda-Sudoh, Bull. Chem. SOC.Jpn., 1978, 51, 1009.
52 P. M. Saatzer, R.D. Koob, and M. S. Gordon, J . Chem. SOC.,Faraday Trans. 2 , 1977, 76, 829.
53 M. S. Gordon, J . Chem. Phys., 1978,69, 4955.
54 Y. Hatano, T. Nomura, and K. Tanaka, Znt. J . Quantum Chem., 1978, 13, 207.
55 Y. Hatano, Chem. Phys. Lett., 1978, 56, 314.
10 Photochemistry
X'Z', and C ' C - , A'n, and E'Z' excited states of SiO have been p ~ b l i s h e d . ' ~
There is a considerable amount of spectroscopic information available for this
molecule. SiO is of interest in astrophysics as it occurs in stellar atmospheres and
plays an important role in the functioning of SiO, heat shields used on Jupiter
probes.
A theoretical model of the B'3Zu- and B3ngstates of N, has been used to describe
accurately (to 0.01 cm- ') recent high-resolution spectroscopic data and the
-, ''
contribution of third-order terms to the calculation of vertical excitation energies
with the equations of motion - Green's function- methods has been investigated
with a study of N,.58 A b initio SCF MO calculations of the low-lying states of
linear symmetric N,- and of bent N,- have been performed with the intention of
explaining the absorption and fluorescence spectra of alkali aides. The results ''
provided a good qualitative description of the excited states, but the quantitative
agreement was poor.
A b initio calculations of the excited states of 0, have been published.60 The
change in the character of the lowest two ,&,- states with internuclear distance r
was investigated by CI calculations with an extended STO basis set. The chosen
reference functions were found to give an adequate description of the two states
around the ground-state equilibrium internuclear distance, re = 2.3 a.u., but to be
grossly inadequate for distances greater or smaller than re. At small values of r the
lowest state, the B state, is Rydberg in character, but this slowly changes to
valence character as r increases. The higher E3&- state has an even stronger
distancexharacter dependence, going from Rydberg to valence, to Rydberg, and
finally to valence character as r increases from 1.9 to 3.1 a.u. Accurate measure-
ments of the absorption and excitation spectra of 0,- in low-temperature NaCl
crystals, where it is a stable substitutional impurity, have enabled comparisons to be
made of the experimentally determined potential-energy curve for the first excited
state 'nu with the results of recent calculations. 6 1 Extensive ab initio CI calculations
of potential energy surfaces in ozone have given the geometries and relative energies
of the nine lowest states in C,, symmetry.62The agreement of the experimental and
theoretical properties for the ground state was significantly better than in earlier
calculations as a result of an improved basis which included 3d polarization
functions; of the excited states only the ,B, state was predicted to be a bound state
and then only by 0.21 eV. Such a state has not been observed experimentally. The
correlation diagram of the states of 0 , with those of 0, + 0 is shown in Figure 4.
Large-scale CI calculations of the electronic states of 0,and 0,' over a larger
energy range have also appeared.63 They were able to reproduce a number of the
features of the 0 , spectrum, including the first three ionization potentials found in
earlier photoelectron spectroscopy work. The application of the SCF X , Scattered-
56 S. R. Langhoff and J. 0. Arnold, J . Chem. Phys., 1979, 70, 852.

57 E. J . Beiting, tert., C. C. Jones, and W. Benesch, J . Mol. Spectrosc., 1978, 70, 108.
58 D. L. Yeager and K . F. Freed, Chem. Phys., 1977, 22, 415.
59 A. R. Rossi and R. H. Bartram, J . Chem. Phys., 1979, 70, 532.
6o H. Tatewaki, K. Tanaka, F. Sasaki, S. Obara, K. Ohno, and M . Yoshimine, Int. J . Quantum Chem.,
1979, 15, 533.
6' J. Rolfe, J . Chem. Phys., 1979, 70, 2463.
6z P. J . Hay and T. H . Dunning, jun., J . Chem.'Phys., 1977, 67, 1290.
63 K. H. Thunemann, S. 0. Peyerimhoff, and R. J . Buenker, J . Mol. Spectrosc., 1978, 70, 432.
O3 STATES
0 +02 TRIPLET SINGLET 0 +o*
-? z
\
w
-6
's +
-5
-4
'D +
-3
3P +
3P +
-2
3P +
-I
Figure 4 Correlation diagram of the states of 0 , at the ground-state geometry (verticfe)and

optimum C,, geometries (adiabatic)with the states of 0, + 0
(Reproduced with permission from J . Chem. Phys., 1977,67,2290)
Wave method to the theoretical treatment of Rydberg and valence states in small
polyatomic molecules is illustrated by a study of the excited states of H,S.64 It is
suggested that this method is more flexible in such calculations than either the one-
centre expansion methods or the LCAO (multi-centre) methods, and the results, for
H,S at least, indicate that it is sufficientlyaccurate to aid spectroscopic assignments
involving Rydberg states. There is generally good agreement between the results
and those of a recent large-scale ab initio CI study. 6 5 A CNDO CI method has been
used to calculate the electronic spectrum of SO, and thereby aid in the
interpretation of phosphorescence microwave double-resonance and microwave-
induced delayed phosphorescence experiments on this molecule.66
A pseudopotential technique has been used to calculate the vertical transition
energies of the iodine molecule. Strong mixing of the valence configurations of the
same symmetry was found to be important, particularly for the %+, ng,and nu
states. Despite the lack of diffuse orbitals in the basis set and the neglect of
spin-orbit coupling there is quite good agreement with measured transition
energies. A new 'non-Mulliken' state, 3q+, was predicted in the 9eV region, and
"
R. Roberge and D. R. Salahub, J . Chem. Phys., 1979, 70, 1177.
65
S. Shih, S. D. Peyerimhoff, and R. J. Buenker, Chem. Phys., 1976, 17, 391.
'' B. Minaev, T. 0. Tlepbergenov, and Z. M. Muldakhmetov, Opt. Spektrosk., 1978,45, 679.
6'
C. Teichteil and J. P. Malrieu, Chem. Phys. Lett., 1977, 49, 152.
12 Photochemistry
the inclusion of diffuse AOs is expected to lower its energy. The excited-state
potential curves of fluorine have been investigated by the asymptotic method. 6 8
A new experimental technique to measure the spectroscopic properties of
excimer molecules has been applied to Hg,.69 A theoretical treatment of diatomic
excimer molecules has been used to interpret the results. 70 The resulting potential-
energy curves and transition rates have been used to discuss the design of a possible
optically pumped 335 nm (1, + )0', mercury laser. Subsequent time-resolved
fluorescence measurements on this system, to avoid a trimer emission 485 nm, have
made it possible to calculate part of the repulsive wall of the 1, state's potential
surface. 7 1 Ab initio MCSCF-CI calculations on Au, have been published. 7 2 The 68
core electrons were replaced by an averaged relativistic effective core potential
(AREP). There is generally good agreement between the calculated and experi-
mental values for a number of Au, properties, e.g. the ground-state dissociation
energy and the energies of the allowed 0', and 0', transitions.
To aid in the interpretation of the luminescence properties of ions such as Ti4+,
V5+,Mo6+,and W6+ in an oxidic lattice, SCF-MO calculations on the W 0 , 6 -
octahedron have been ~ n d e r t a k e n As . ~ ~a result of the study the absorption
spectrum is attributed to excitation into two ' T l ustates and the luminescence to
emission from two 3Tlustates. Ab initio SCF CI calculations have been performed
to describe the ground and excited states of CrCl,(g), CoCl,(g).74 The results
provided a good basis for the interpretation of the spectra of these gaseous
transition-metal dichlorides.
A series of SCF calculations on ethylene have been carried out, in which the basis
set is systematically altered by a change in the number of diffuse orbitals.75As a
result of this the number of members of the Rydberg series [ ( q n n ? ) in the model
used] will change, but there would be little effect on the location and character of
valence-like (n-n?) states, cf. the stabilization method of resonant scattering. Such
a stable state was in fact found, at 10.21eV with a large oscillator strength of 0.46,
and it is believed to be the analogue of the spectroscopic V ( ' B J state found in
Hartree-Fock theory and observed experimentally at 7.66 eV. These 'resonances'
that are spuriously pushed into the continuum in SCF theory may occur in other
systems. CI calculations on all the n = 3 Rydberg states of C,H, derived from the
excitation of the electron have been performed, and with one exception, the 8.26 eV
transition, the results are in agreement with the spectral assignments of Mulliken. 7 6
The recent application of the DODS(different orbitals for different
spins)-NO(natura1 orbital) CI method to the ground state of unstable molecules
such as the trimethylene diradical has led to an investigation of its use for unstable
excited states, using planar and perpendicularly twisted forms of substituted
'* G. V . Shlyapnikov and I . P. Shmatov, 0 p 1 . Spektrosk., 1978, 45, 487.

69 R. E. Drullinger, M. M . Hessel, and E. W. Smith, J . Chem. Phys., 1977, 66, 5656.
O
' E. W. Smith, R . E. Drullinger, M. M. Hessel, and J . Cooper, J . Chem. Phys., 1977, 66, 5667.
71 M . Stock, E. W. Smith, R. E. Drullinger, and M. M. Hessel, J . Chem. Phys., 1978, 68, 4167.
72 W. C. Ermler, Y. S. Lee, and K . S. Pitzer, J. Chem. Phys., 1979, 70, 293.
73 A. B. van Oosterhout, J . Chem. Phys., 1977, 67, 2412.
74 C. D. Garner, I . H. Hillier, and C. Wood, Inorg. Chem.. 1978, 17, 168.
75 C. F. Bender, V. McKoy, and E. R. Davidson, J . Chem. Phys., 1977, 67, 2178.
7h L. E. McMurchie and E. R . Davidson, J . Chem. Phys., 1977, 67, 5613.
ethylenes as examples. 77 A brief review of the excited states of the ethylenic bond
has been published. 7 8
An interesting paper has appeared that investigates the so-called 'sudden-
polarization' effect in s-cis, s-trans diallyl, using both semi-empirical and ab initio
methods. 7 9 In this effect a strong charge separation occurs between the low-lying
singlet excited states in the two moleculai fragments resulting from the rupture of
an olefinic double bond. The paper considers several approaches to explain the
possible origins of such an effect. Starting with a description of the diallyl as an
alternant system, non-alternancy is introduced by considering (a) the effect of
different electronegativities for each carbon atom in the conjugated system and (b)
the effect of introducing hopping parameters which violate the alternant symmetry.
Figure 5 shows the energies of the two lowest polarized states and the deviations
from electroneutrality of the IS,optimized geometry of the trans-allylic triad as a
function of the twist angle O,, for the two effects (a) and [(a) + (b)]combined. A
related study considers butadiene, where the lowest 'n?r*singlet excited states are
stabilized when twisted to 90" around one double bond and become strongly
ionic. Although it was difficult to treat these zwitterionic excited states
theoretically, two general observations were that (i) the positive and negative net
charges attract each other and tend toconcentrate on either side of the double bond
and (ii) that the Q polarization effect stabilizes these localized structures and
diminishes the net charges. The paper extrapolates these ideas in a very interesting
manner to consider the case of retinal and its protonated Schiff base. A
renormalized CI method has been developed to account correctly for the excited-
state correlation in SCF calculations of the n-electron systems of polyenes. The ''
method gives results in excellent agreement with more extended CI calculations,
particularly for the 'B,+, ,BU+, and ,A,+ states. A relation between the bond length
and the bond order has been determined for a model of a singlet excited state of a
polyene which adjusts its bond lengths relative to the ground state to achieve
stabilization.82In a study that is of particular interest to the process of cis-trans
photoisomerization, the twisting-force constants for the ground and excited states
of linear polyenes have been calculated for the cases of ethylene up to dodeca-
h e ~ e n eA. ~CNDO
~ method was used with perturbation theory to second order.
Large-scale CI calculations of the low-lying singlet and triplet states of
cyclobutadiene for square, rectangular, rhomboid, and trapezoidal structures have
broadly confirmed the results of earlier ab initio studies. 84 The lowest-energy singlet
rectangular structures interconvert through a square intermediate. The barrier to
interconversion is high (12kcalmol- ') but is still low relative to any routes
involving rhomboid distortion. Similar conclusions were reached in ab initio MO
calculations with full n space, CI, using a basis set of STO-3G orbitals.*' The
77 K. Yamaguchi, S. Yabushita, 0, Minokaura, and T. Fueno, Chem. Phys. Lett., 1977, 59, 303.
78 G. Trinquier, Actual. Chim., 1978, 5 , 20.
79 V. Bonacic-Koutecky, J . Cizek, D . Doehnert, and J. Koutecky, J . Chem. Phys., 1978, 69, 1168.
M. C. Bruni, J. P. Daudey, J. Langlet, J. P. Malrieu, and F. Momicchioli, J . Am. Chem. SOC.,1977,99,
3587.
I. Ohmine, M. Karplus, and K. Schulten, J . Chem. Phys., 1978,68, 2298.
K. Nakachi, M . Sakuranaga, and H. Suzuki, J . Phys. SOC. Jpn., 1977, 43, 272.
83 H. Nagae, J . Phys. SOC.Jpn., 1978, 44, 1329.
84 J. A. Jafri and M. D . Newton, J . Am. Chem. SOC.,1978, 100, 5011.
W. T. Borden, E. R. Davidson, and P. Hart, J . Am. Chem. Soc.. 1978, 100, 388.
14 Photochemistry
E/eV + e/tv
-9.910. -9.750.
-9.920. -9.760-
-9.9 3 0 - -9.770-
q
l-
'
n
-1 lnU----F BT &B8 9 9v 9 9T 9s,
3
Figure 5 'Suddenpolarization' ofjirst and second singlet excited states of s-cis-, s-trans-diallyl
with ' S , optimizedgeometry '. The energies of two lowest polarized states S , ( I )and S,(II) and
corresponding deviations from electron neutrality of the trans allylic triad as a function of the
twist angle 034. ( a ) Approach 2 parametrization l(A + B ) corrected for the bond lengths
R j s j + ,j?j,j+l
: = -59.243 exp (-2.206 R j , j + , withj
) = 1, 2, 4, 5 , and j?34 = -59.243
exp( -2.206 R 3 4 ) ~ ~ ~(b) 0 3Approach
4; 4 withparametrization l(A + B + C ) corrected in
the same way
(Reproduced with permission from J. Chem. Phys., 1978, 69, 1168)
results cast doubt on the interpretation of the i.r. spectrum of the matrix-isolated
parent [4]annulene.
Extensive ab initio generalized valence-bond (GVB) and CI calculations on the
valence excited states and positive ion states of trans- 1,4-butadiene and all-trans-
1,3,5-hexatriene have been published. 8 6 The agreement with experimental values is
good. The sudden polarization effect in the excited states of 1,3,5-hexatriene has
been investigated using MO calculations with full orthogonal valence-bond
structures.'' The effect is attributed to an avoided crossing of two excited states. A
study, using ab initio MO theory, of hydrogen bonding in the ground and low-lying
86
M . A. C. Nascimento and W. A. Goddard, tert., Chem. Phys., 1979, 36, 147.
*' C. M . Meerman-van Benthem, H. J. C. Jacobs, J. J . C. Mulder, N o w . J . Chem., 1978, 2, 123.
excited states of the formic acid dimer has been published.88An extension of the
electron-hole potential (EHP) method to a two-configuration wave function was
used, in which form it is the simplest version of the MCSCF method.
Notwithstanding the complication introduced by the resonance interaction of the
two identical dimer subunits the results are of relevance to proton exchange
between base pairs in nucleic acids. No evidence for a lowering of the barrier to a
concerted transfer of the two bridging protons on going from the ground to the
lower excited states was found. It was noted, however, that in the 'A'( II -, li") state
of formic acid an n or 0 -+ a* configuration becomes important as the 0,-H,
distance increases, and this may result in the dimer 'A, or 'B, states (not studied, as
an MCSCF calculation would be required) having a lower barrier than the lower-
lying excited states. The correct order and symmetry of the ground, 'A1, and
',
excited, 3A 2, 'A , 3A states of formaldehyde were obtained in calculations using
'
the semi-empirical CNDO/VN- method,89 and a CND0/2-CI method has been
used to investigate the charge distributions in low-lying exciting states of
diacetamide and N-methyldia~etamide.~' The latter paper follows a study by the
authors of low-lying excited states for different conformations of diformamide and
N-methyldif~rmamide.~' As reported in my chapter in Volume 9 of this title, ab
initio SCF calculations on the interesting glyoxal molecule were not satisfactory. In
particular the 3A, state was predicted to have an adiabatic excitation energy, T,, of
',
36900cm- some 7700cm- ' above the well known experimental value, and an
unusually large splitting of the 1B,( I I - ~ * ) state in trans-glyoxal placed it between the
(n-fl), 3A, and 3B,, states. A new study of trans-glyoxal with ab initio correlated
wavefunctions has given significantly better agreement with experiment. 9 2 The 3A,
',
state is predicted to have a T , of 21 700cm- and the inclusion of electron
correlation is found to reverse the SCF ordering of the 3B, and 'B, states at the
vertical geometry. A similar change in the ordering of these states was also bound in
another study which included CI.93The authors suggest that the two lowest-lying
triplets, 3A, and 3Bu, are close enough to be in thermal equilibrium. SCF-Cl
calculations of the low-lying excited n7ir states of a series of carbonyl compounds 94
and a non-empirical SCF-MO study of the lowest-triplet-state potential-energy
surface of thiocarbonyls 9 5 have been published.
Various discrepancies between theoretical and experimental work on the U.V.
spectroscopy of the HCN molecule have been further investigated by ab initio SCF
and CI methods, which have been successfully applied to a number of small
molecules, to calculate excitation energies and by apriori methods to calculate the
vibrational structure. 9 6 The results confirm a previous reassignment on theoretical
grounds of the upper state in the a t X band system as a 1'A"-'C- species and not
S. Iwata and K. Morokuma, Theor. Chim. Acta, 1977, 44, 323.

E. I. Cheglokov, A. F. Terpugova, B. F. Samsonov, and V. A. Kilin, Izv. Vyssh. Uchebn. Zaved., Fiz.,
1978, 21, 43.
90 J. Maranon and 0. M . Sorarrain, Z . Phys. Chem. (Leipzig), 1978, 259, 635.
9' J . Maranon and 0. M. Sorarrain, An. Asoc. Quim. Argent., 1977, 65, 63.
92 C. E. Dykstra, R . R. Lucchese, and H . F. Schaefer, tert, J . Chem. Phys., 1977, 67, 2422.
93 W. B. Mueller, J. F. Harrison, and P. J. Wagner, J . Am. Chem. Soc., 1978, 100, 33.
94 N . Tyutyulkov and G. Neikov, Izv. Khim.. 1977, 10, 313.
9s P. G . Mezey, R. P. Steer, and A. Kapur, J . Photochem., 1978, 9, 130.
96 M. Peric, S. D. Peyerimhoof, and R . J. Buenker, Can. J . Chem., 1977, 55, 3664.
16 Photochemistry
A’ as originally suggested. The angular potential curves for the low-lying states of
HCN are shown in Figure 6. A similar SCF CI study of HCN that considers the first
four excited singlet states has been p~blished.~’A
review of the electronic structure
of the ground and excited states of the cyanoto and thiocyanoto groups has
€/hart ree
0.40 -
0.35 -
0.32-
0.28 -
0.2L - I
0.20 -
0.16 -
Figure 6 Angular-potential curves for the low-lying states of HCN obtained from the CI
calculations. The calculated vibrational levels are also indicated
(Reproduced with permission from Can. J . Chem., 1977, 55, 3664)
appeared. 98 Extended Huckel calculations have been used to develop a theoretical

model of the photochemical and spectroscopic properties of hexacyano- and
pentacyano-ferrate complexes with nitrogen-containing aromatic l i g a n d ~The .~~
electronic excitation energies and ionization energies of the hexacyanocobaltate(II1)
anion have been calculated using the all-electron SCF multiple-scattering (MS-Xar)
method. loo
Theoretical work has predicted that for the pair of isomers HSiN and HNSi the
latter is easily the more stable. This contrasts with the pair of analogous carbon
isomers where HCN is more stable. A recent paper contains a study of the
electronically excited states in the two silicon isomers, using ab initio methods. l o
The (z,e) states were found to prefer somewhat bent nuclear configurations,
whereas the ground and most (qe) states have a linear equilibrium nuclear
arrangement. The dipole-allowed transition to the ‘n species from the ground state
of HNSi is predicted to be at 7.3eV.
91 G. J. Vazquez and J . F. Gouyet, Chem. Phys. Lett., 1978, 57, 385.
98 K.Wittel, J. L. Meeks, and S. P. McGlynn in ‘Chemistry of Cyanates and their Thio Derivatives’, ed. S.
Patai, Wiley, Chichester, England, 1977, Vol. I, p. 1.
’’ G. Calzaferri and F. Felix, Helv. Chim. Acta, 1977, 60,730.
loo A. Goursot, E. Penigault, J. Weber, and J . G . Fripiat, N o w . J . Chim., 1978, 2, 469.
lo’ R . Preuss, R . J . Buenker, and S. D . Peyerimhoff, Chem. Phys. Lett., 1979, 62, 21.
The formamide molecule is of considerable theoretical interest as it is the simplest
amide and as such is the key to understanding the spectroscopy of polypeptides.
Previous theoretical studies have neither clearly determined the order of nn* and
n71* triplet states nor agreed on their energies, which may be low enough for them to
act as energy sinks or routes for energy transfer in proteins. The studies have also
predicted values for the xn* energy considerably higher than the experimental
assignment to a transition at 7.32 eV. New ab initio calculations on formamide have
been published that predict the triplet energies to be 5.4 eV ( 3n7ic)and 5.8 eV ( 3nn*)
and give better agreement for the 'nn* state. ' 0 2 Related results are contained in a
paper which also contains calculations of the vertical ionization energy of
formamide. '03 The measured vibrational frequencies of di-imide (N 2H2)have been
compared with those calculated from new ab initio CI calculations of the potential-
energy curves of the ground and '(n,n*) excited states. The six vibrational
frequencies are calculated for the two cases in which they are either independent '04
or coupled together. lo' There is a considerable improvement in the latter case, the
'
agreement being better than 100cm- for all the cases where comparison can be
made.
Force fields have been calculated for in-plane and out-of-plane vibrations of the
first excited singlet electronic state, 1B2u,of benzene.'06 The accuracy of the
predicted frequencies is indicated by the good agreement between the calculated
(198 cm- ') and experimental (203 cm- ') values for the shift of the origin of the
'BZu+ ' A lg electronic-absorption band on going from [ 'H Jbenzene to
[2H6]benZene.A CNDO/S method with CI has been used to calculate the transition
energies and oscillator strengths of the ct-, p - and pbands of benzene, pyridine, and
the eleven fluorobenzenes with mixed success. l o 7 In contrast, calculations of the
electronic excited states of benzene, using the INDO/S basis, which, unlike the
CNDO method, does not give a zero value for the energy separations of both the
an* and na* states, show reasonable agreement with previous ab initio calcu-
'
lations. O 8 The three benzyne (bisdehydrobenzene) isomers have each been
suggested as intermediate species in organic reactions. There is no common
agreement as to the nature of the lowest energy state or equilibrium geometries in
the isomers, but there is some hope that their relative stabilities will be measured in
ion cyclotron resonance experiments. Ab initio calculations using an extended basis
(4-31G) of atomic mbitals have predicted that each of the three isomers has a singlet
ground state and that the total energy increases in the order
ortho < meta < para. l o g The singlet meta- and para-isomers were found to have
diradical character, whereas the orzho form was aryne-like. CNDO/S CI calcu-
lations on various conformations of 1,l '-binaphthyl have strongly supported the
idea that there is a cis + trans rotation about the interconnecting bond to equal or
lo' L. Z. Stenkemp and E. R. Davidson, Theor. Chim. Acta, 1977, 44, 405.
'03 E. Oliveros, M . Riviere, C. Teichteil, and J.-P., Malrieu, Chem. Phys. Lett., 1978, 57, 220.
'04 M . Peric, R. J. Buenker, and S. D. Peyerimhoff, Can. J . Chem., 1977, 55, 1533.
'05 M . Peric, R. J. Buenker, and S. D. Peyerimhoff, Mol. Phys., 1978, 35, 1495.
lo' M. J . Robey and E. W. Schlag, J . Chem. Phys., 1977, 67, 2775.
lo' D. Bhaumik and G . S.Kastha, Indian J . Phys., 1977,51B, 195.
Io8 H. H o and Y. J. Ihaya, Bulf. Chem. SOC.Jpn., 1977, 50, 1629.
Io9 J. 0. Noell and M. D. Newton, J . Am. Chem. SOC.,1979, 101, 51.
18 Photochemistry
'
less planarity on going from rigid to fluid solutions. This change can account for
the fluorescence shift, the decrease in the fluorescence lifetime, and the appearance
of several S, t S, transitions observed experimentally. The excited-state equilib-
rium geometries of biphenyl, 1,I '-binaphthyl, and fulvalene have been calculated by
use of a method that combines a PPP n-method with an empirical a-potential,'"
and the bonding between benzene-benzene and anthracene-benzene dimers in
ground and excited electronic states has been calculated from MO theory. ' l 2
It is still not practical, for reasons of time and expense, to apply the most accurate
computational procedures presently available to large molecules, and the search for
approximate methods continues. A study of the low-lying excited electronic states
of pyrazine has explored the use of ab initio CI calculations in which CI expansions
are generated from SCF calculations, using a small set of floating spherical
'
Gaussian orbitals (FSGO). l 3 Pyrazine was chosen for the study because of the
presence of several types of electronic states [ 'l3(n -+ n*), ' * 3 ( n .*)I and the
-+
availability of experimental data and results from a number of previous high-

quality CI studies. The method was found to give an ordering of the states which is
substantially correct, and as in other calculations (see reference 115 ) a linear
relation was found between the calculated Franck-Condon transition energies and
those found experimentally. A semi-empirical calculation of the excited states of
'
azabenzenes has been published which uses the VN- potential method. ' l 4 An
interesting paper has applied the methods cited in reference 113 to N-
methylcarbazole."' Again the correct ordering of states is given and a linear
60
p 5.0
3.0
-
III
C
e
d
20
0
c
E 10
.-E
L
e
g
w
o
Calculated transition tnergy/cV
Figure 7 A plot of experimental vs. calculated (CI)transition energiesfor singlet states in N-
methylcarbazole
(Reproduced with permission from J. Am. Chem. Soc., 1978, 100, 1371)
'lo R. W. Bigelow and R. W. Anderson, Chem. Phys. Lett., 1978, 58, 114.
''I
J. Suehnel and K. Gustav, Z . Chem., 1977, 17, 417.
I"
V. A. Zubkov, Teor. Eksp. Khim., 1977, 13, 527.
'I3
J. D. Petke, R. E. Christoffersen, G . M. Maggiora, and L. L. Shipman, Znt. J . Quantum Chem.,
Quantum Biol. Symp., 1977, 4, 343.
B. F. Samsonov, A. F. Terpugova, and E. I. Cheglokov, Teor. Eksp. Khim.. 1977, 13, 106.
'I5 D. Murk, L. E. Nitzsche, and R. E. Christoffersen, J . Am. Chem. SOC.,1978, 100, 1371.
relation between calculated and experimental transition energies for the first four
singlets was found, and this is illustrated in Figure 7. It is not expected that this
linear relation will hold for states with substantial Rydberg or ionic character, but it
clearly has some potential for predicting the location of states, particularly in large
molecules. Ab initio SCF MO and n-electron CI calculations of the n-n* excited
states of the pyrrole molecule were found to give results in good agreement with
'
experiment. ' The spatial extension of the wavefunctions indicates that the
ground and lowest 3B2and 3A (an unobserved triplet state 1.10eV above 3B2,the
lowest excited state) states and the first excited 'A state are valence-type and the
first and second 'B2and the second 'A state are Rydberg stages. MO calculations
on fulvene have indicated that electronic excitation both to the first singlet and to
the first triplet states corresponds to a charge transfer from the exocyclic carbon to
the ring. l 7
SCF MO LCAO and INDO calculations on lithium aryls have indicated that
their behaviour may be attributed to an unusually low singlet-triplet energy
separation. ' l 8 The rotational constants of benzaldehyde in its first excited triplet
state have been calculated and compared with experimental values. The '
possibility that the lowest excited singlet state of polyenes is 'A, and not 'B, has
been explored in n-electron PPP calculations on a series of 1-arylbutadienes. 2o The '
results indicate that a weakly allowed 2 'A,-like state lies below the allowed 1 'B,-
like state in 1-arylbutadienes but that in unsubstituted or symmetrical diphenyl-
substituted polyenes it is the 1 'B, state that is lowest. The charge densities in the two
states are quite different, and this should result in significant differences in their
photochemical behaviour. The all-valence electron approximation was used in
calculations of the spectroscopic properties of acene quinones, 2 1 and an HF '
method has been used tacalculate the excitation energies and transition moments of
polyacene radical ions. 122
A useful rule has been identified to account for the effect of the hydroxyl-group
position in various isomeric hydroxycoumarins on their fluorescence properties.
This follows from semi-empirical SCF calculations on the excited states of
'
hydroxycoumarins. 23 To aid the interpretation of electron-spin polarization
measurements in the charge-transfer system phenanthrene-pyromellitic acid
dianhydride (PMDA), ab initio MO SCF calculations on the ground and low-lying
excited states of PMDA have been carried out, the first on this molecule. 124 LCAO
MO calculations have appeared of various properties of the ground and first excited
state of the boron-nitrogen ring compounds which are the analogues of the carbon
compounds biphenyl and biphenylene. 2 s '
'I6
K. Tanaka, T. Nornura, T. Noro, H. Tatewaki, T. Takada, H. Kashiwagi, F. Sasaki, and K. Ohno, J .
Chem. Phys., 1977, 67,5738.
'I7 N . Tyutyulkov, G . Neikov, and I. Kynev, Teor. Eksp. Khim., 1977, 13, 386.
'I8
I. A. Abronin, A. Ya Shteinshneider, G . M. Zhidomirov, and F. M . Stoyanovich, Izv. Akad. Nauk
SSSR. Ser. Khim.. 1979, 307.
'I9
S . N . Thakur, Indian J . Phys., 1977, 51B, 184.
P.J. Baldry and J. A. Barltrop, Chem. Phys. L e f t . , 1977, 46, 430.
G. Olbrich, 0. E. Polansky, and M . Zander, Ber. Bunsenges. Phys. Chem., 1977, 81,692.
''' A. V. Luzanov and V. E. Umansku, Zh. Strukt. Khim., 1977, 18,3.
W.Fabian, Z . Naturforsch., Teil, B, 1978, 33B,628.
C.P. Keijzers, P. S. Bagus, and J. P. Worth, J . Chem. Phys., 1978, 69, 4032.
125 E. Y. Bolycheva, V. N . Mochalkin, and A. B. Bolotin, Liet. Fiz. Rinkinys. 1977, 17,41.
20 Photochemistry
The results of CND0/2 MO calculations on the first (n,rl")excited singlet and
triplet states of the pyrimidine bases thymine, uracil, and cytosine have indicated
that the C-5+-5 bond in each of them should be very reactive.'26 Huckel
calculations in the same paper, on the ground- and excited-state energy levels of
non-covalent pyrimidine dimers in sandwich-type structures, indicated that
excimer formation was a possibility for all three bases. PPP MO calculations have
been used to investigate the 7t-electron distribution in the excited state of the
'
fluorescent cytosine derivatives ethenocytosines. *' The n-electron distribution in
the first excited singlet and triplet states of cytosine indicates that electrostatic
bonding may play an important role in the formation of thymine and cytosine
photodimers (see reference 126). This emerges from a CNDO CI study that also
suggests that the possibility of proton tunnelling in the guanine-cytosine base pair
of DNA is reduced if the excitation energy is localized on cytosine. 12' The use of
intermediate excitons in the theoretical description of electronically excited states in
polymers has been illustrated by a study of two simple periodic DNA models,'2g
and the applicability of semi-empirical RPAs has been investigated by calculating
the excited states of DNA bases.'30
Recent work (1972-1976) on quantum-chemical calculations on photoreceptor
''
pigments has been briefly reviewed. One of the disadvantages of using the PPP
method is the difficulty in understanding the wavefunctions that are obtained. A
procedure called configuration analysis (CA) overcomes this difficulty by expres-
sing the SCF molecular orbitals as linear combinations of a set of reference orbitals,
and obvious choice for which would be isoconjugate-hydrocarbon orbitals or
localized orbitals. The CA method has been applied to the photobiological
receptors luciferins, chlorophyll a, and the 11-cis-retinal Schiff bases 1 3 * and to
chlorophylls, phytochrome, and stentorin. 33 The results show, amongst other
things, that in chlorophyll a the peripheral C = C and isocyclic C = O groups are not
locally excited to any significantextent, and this is also true for the 11-C=C bond of
rhodopsin. The simple free-electron molecular-orbital (FEMO) method has been
used to study the electronic structure of chlorophylls. 13'The ab initio methods that
involve the use of a basic set of FSGOs and that were mentioned above in
connection with studies on N-methylcarbazole and pyrazine have been applied to
magnesium porphine and porphine 1 3 5 and to magnesium chlorin and chlorin.
The results reveal a complex pattern of excited states which are used to analyse the
electronic absorption spectra of these molecules. The ground and excited states of
porphyrin, 2,4-divinylporphyrin, and a$, y,Stetraphenylporphyrin have also been
V. I. Danilov and N. V. Zheltovsku, Mol. Genet. Giofiz., 1976, I , 10.

12' A. A. Kost, and S. V. Ermolin, Nucleic Acids Res., Spec. Publ., 1978, 4, 197.
P. C. Mishra, Indian J . Biochem. Biophys., 1977, 14, 214.
lZ9 M. Kertesz, Kem. Kozl.. 1976, 46, 393.
I3O
H. Ho and Y. J . I'Haya, Chem. Phys. Lett., 1976, 38, 271.
13' H. Suzuki and H. Kobayashi, Photochem. Photobiol., 1978, 27, 815.
13' C.-A. Chin and P.-S. Song, Int. J . Quantum Chem.: Quantum Biol. Symp., 1976, 3, 89.
133 P.-S. Song, C.-A. Chin, and I. Yamazaki, Int. J . Quantum Chem.: Quantum Biol. Symp.. 1977,4305.
L. Skala and E. Vavrinec, Stud. Biophys., 1978, 72, 39.
135 J. D. Petke, G . M. Maggiora, L. L. Shipman, and R. E. Christofferesen, J . Mol. Spectrosc.. 1978,71,
64.
'36 J. D. Petke, G. M. Maggiora, L. L. Shipman, and R. E. Christoffersen,J . Mol. Spectrosc., 1978,73,
311.
calculated.137A semi-empirical CND0/2 MO method was used for the ground
states and a CNDO/S CI method for the excited states.
The semi-empirical CNDO/S method has also been used to calculate the spectral
properties of 11-cis-N-methyl protonated retinylidene Schiff base-C,H, com-
plexes. 13* When retinal binds to its apoprotein opsin to give rhodopsin there is an
unusually large bathochromic shift to give the main rhodopsin peak at 500 nm.
This shift has attracted considerable theoretical attention to try and identify the
-
interaction responsible for the shift. There is a growing body of evidence that there
may be a more or less specific interaction of the Ir-electrons of the polyene with a
nearby aromatic amino-acid residue, and this is investigated in the paper by placing
a benzene moiety at various orientations along the chain. This simple model was
able to produce significant spectral shifts whose origin was a charge donation to the
chain from the benzene. The same problem has been considered in another paper in
which a dielectric medium is intended to mimic the aromatic side-chain residues.
The shift is attributed to an attractive coupling of the electrons in the polyene and
relates to a theory of macromolecular superconductivity. 39
A simplified model of the active site of the simplest iron-sulphur protein
rebredoxin has been used as a basis for ab initio calculations of the ground and
excited states of this system.14' This has led to the complete assignment of all the
spectral features below 3eV of this chromophore, in which an iron atom is
tetrahedrally surrounded by four cysteine sulphur atoms. Both the oxidized and
reduced forms of the protein are treated, and it is shown that the ground state in
each of them is high-spin. It is also shown that the calculated charge distributions
are in agreement with the results of Mossbauer studies. Tables l a and 1b summarize
the results from this important paper which the authors believe is the most
comprehensive ab initio study of a transition-metal complex yet published.
3 Absorption Spectroscopy
General Theory.-There have been some very interesting discussions of the
Born-Oppenheimer (BO) separation in the recent literature. The BO separation is a
cornerstone of theoretical physics and is central to working concepts in spectros-
copy. It is very interesting, however, to return to basics and to see where other
constructions lead and where they can provide new insights into the behaviour of
molecules. For example it has been suggested that the natural co-ordinates for a
separation of the motion in a neutral molecule are those of the collective motion of
neutral subsystems, e.g. bonds, and the individual internal motion in each
subsystem, rather than the nuclear and electronic co-ordinates. 4 1 The physical '
reason for the separation arises from a division of the potential energy into two
parts and has nothing to d o with the smallness of the mass ratio, me,/mnu,as is
commonly believed. The adiabatic approximation, in which nuclei are regarded as
classical point masses following time-dependent paths and the electronic state is
13' S. J . Chantrell, C. A . McAuliffe, R. W. Munn, A . C. Pratt, and R. F. Weave, Bioinorg. Chem., 1977,7,
283.
13' M . Muthukumar and L. J . Weimann, Chem. Phys. Lett., 1978, 53,436.
13' L. J. Dunne, Jerusalem Symp. Quantum Chem. Biochem., 1977, 10, 187.
140 R. A. Bair and W. A. Goddard, tert., J . Am. Chern. SOC.,1978, 100, 5669.
14'
H. Essen, Int. J . Quantum Chem., 1977, 12, 721.
h,
N
Table l a Excited states of the reduced model Fe(SH),*- (energies in eV)

d-configuration Fe(SH),' - calculated (Et4N)2[Fe(S2-o-xYl)21a Rubredoxin
X2- transition excitation oscillator excitation excitation
state z2 y2 xy yz xz spin type energy (Cl) strength v> energy E / M - cm- ' energy E/M- cm- '
I 2 1 1 1 1 2 g.s. 0'
I1 1 2 1 1 1 2 d-d 0.17 2.5 x lo-' ~ 0 . 1 1 ~ -O.lld
111 1 1 2 1 1 2 d d 0.32 1.1 x 10-4 60.50
IV 1 1 1 2 1 2 d-d 0.61 1.6 x G0.62 109, sh 0.68-0.87 130
V 1 1 1 1 2 2 d-d 0.62 1.6 x 10-4 0.69 123 ) (f = 9.6 x
10-4)*
VI 2 2 1 1 0 1 d-d 2.79
VII 2 2 1 0 1 1 d-d 2.80
VIII 2 1 2 0 1 1 d-d 2.97
1 2.6-3.0 390
IX 2 1 2 1 0 1 d-d 2.99
X 2 2 0 1 1 1 d-d 3.03
XI 2 2 2 0 0 0 d-a' 4.03
'0.62 and 0.69 bands in MeCN, 2 . 6 3 . 0 band in DMF. C . pasteurianurn, D,O. 'Total energy -65.2748 hartrees (CI); energy of SCF calculation -65.2441 hartrees
(averaged over the five quintet states). dEstimated from the temperature dependence of the quadrupole splitting AEQ(T) = AEq(0)tanh(A2kT).
Q
Table l b Excited states of the oxidized model Fe(SH),- (energies in eV)
a
Fe(SH), - calculated Y
s
&Configuration excitation oscillator (Et4N)[Fe(S2-o-xyl)21” Rubredoxinb 0
X2 - xz+ x z - transition energy strength excitation excitation fb
z2 y 2 x y y z yz‘ spin energy E/M- cm ~ energy E/M- cm-
State type (CO u> z.
I 1 1 1 1 1 5/2 g.s. Od E
b
I1 2 1 1 1 0 3/2 d-d 0.98
I11 1 2 1 1 0 3/2 d-d 1.08
G
2
CI
IV 1 1 2 1 0 3/2 d-d 1.44
V 1 1 1 2 0 3/2 d-d 1.58 1.66 360
VI 1 1 1 1 1 3/2 spin flip 1.90 ( = 0.0025)b
VII 2 1 1 1 1 5/2 LMCT 2.06 1.8-2.0 1500 2.2 14000
VIII 1 2 1 1 1 5/2 LMCT 2.12 0.009
0.024 1 (f= 0.05
0.03f
lxe 1 1 2 1 1 5/2 LMCT 2.32 0.007
X 1 1 1 0 2 3/2 d-d 2.46
XIe 1 1 2 1 1 5/2 LMCT 2.46 2.55 5400 2.53 8850
XI1 1 1 1 2 1 5/2 LMCT 2.55 0.024 1 (f= 0.13 f (f= 0.13 f
0.06)! 0.06) ’
XI11 2 2 1 0 0 1/2 d-d 2.76
‘4 : 1 Me,SO/H,O v/v, aqueous portion 50 mM-trisC1, pH 8.5. C.pusteuriunum,H,O. ‘Considerable ligand haracter is also present. dTotal energy -65.3363 hartrees
(CI); SCF energy -65.2729 hartrees. “These two states have similar Fecharacter but differing ligand character. ’Oscillator strength unitless) may be related to absorbance
(e/M-lcm-’) by f = 4.315 x JE(V)ddii.
h,
w
24 Photochemistry
assumed to adapt itself instantaneously to this motion without any change in the
electronic quantum numbers, is clearly ‘semiclassical’.Other popular concepts such
as potential-energy surfaces, the separation of molecular energies into electronic,
vibrational, and rotational parts, and the symmetry classification of electronic
levels in diatomic molecules all have their origins in the old quantum theory. The
full acceptance of the quantum theory has dramatic consequences even for such a
popular concept as molecular structure. To quote from a recent paper: ‘if we d o not
make molecular structure part of the input of our theory (a full quantum theory) it
will never emerge in the output’. 142 It has been suggested that the retention of the
classical idea of molecular structure is the principal barrier to the development of
‘non-adiabatic’ calculational procedures in which electrons and nuclei are treated
alike.143 (In fact such calculations have recently been carried out on H, and
H2+.144)Whilst the author admits that there are no immediate reasons for
adopting a full quantum theory of molecules, particularly by the experimentalist, it
does appear that some theoreticians are beginning to see a point in the not too
distant future when traditional molecular models will become less and less relevant
to the interpretation of experiments and may even represent a ‘blind alley’.
A theoretical approach to the calculation of molecular spectra which avoids the
BO separation has recently been developed 14” and subsequently applied to
diatomic molecules. 14’’ The theory is the generator co-ordinate method (GCM)
which has its origins in nuclear physics. The theory has no semiclassical features. It
is a non-adiabatic variational method which contains the adiabatic approximation
as a limiting case. It is also possible in the method to separate the total energy into its
electronic, vibrational, and rotational parts, but this is achieved from a purely
quantum-mechanical point of view. The method uses trial functions of the form
given in equation (4),where x represents all particle degrees of freedom and OL a set
W )= Jf(Mx/a)da (4)
of parameters related to the collective motion, which do not appear in the final
result but act as additional co-ordinates to label the basis states and generate the
wavefunctions (hence the GCM). The $ (x) are linear superpositions of continu-
ously labelled basis states x(x/a) with weight functions Aa). The Aa) are deter-
mined from the variational principle and satisfy the secular equation ( 5 ) where
H(a,/?) = ( x ( a ) l H l x ( / ? ) ) and A(.,/?) = (x(a)lx(B)). The eigenvalues of the
c
integral equation, which with an appropriate boundary condition is called the

Griffin-Hall-Wheeler (GHW) eigenvalue problem, are upper bounds to the exact
energies of H . Interested readers are recommended to look at the treatment in
reference 1456 of diatomic molecules based on the above, which as well as deriving
the key result of the separation of energies also illustrates a nice point of detail,
14’ R . G. Woolley, Chem. Phys. Lett., 1978, 55, 443.

‘43 R. G. Woolley, J . Am. Chem. SOC.,1978, 100, 1073.
144 D. M. Bishop and L. M. Cheung, Phys. Rev. A , 1977, 16, 640.
14’ (a) L. Lathouwers, P. van Leuvan, and M. Bouten, Chem. Phys. Lett., 1977,52,439.(6) L. Lathouwers,
Phys. Rev. A , 1978, 18, 18.
namely that of A doubling. In the adiabatic approximation, terms with A # 0 are
doubly degenerate, whereas a small splitting, called A doubling, can be observed
experimentally. This non-adiabatic effect is incorporated in the GCM picture.
A valuable essay has been published that carefully examines the role of
’
molecular-orbital concepts in molecular spectroscopy. 46 The natures of the
different orbital types, i.e. core, valence, and Rydberg, are considered, the
importance of Koopmans’ theorem is stressed, and the question of orbital
interaction which leads to the MO description of charge-transfer excited states,
excimer states, etc, is presented in a unified fashion.
A new approach to understanding the solvent shifting of electronic-absorption
bands that is based on Born’s calculation of the energy of charging an ion in a
dielectric medium has been suggested. 147 The original Born calculation was
extended by several authors to systems of charged particles, and the present paper
uses the form [equation (ti)] due to Jano, 14* where D is the dielectric constant of the
solvent, q is electrostatic charge, and y is a Coulomb integral, to calculate values of

AEe.s.( E E,.,.,,, - E,.,.,J for a series of quinones, using a version of the PPP
method. Forpara-benzoquinone this admittedly crude electrostatic model correctly
predicts the first n-# band to be strongly red-shifted, and for the next n-# band it
predicts a blue shift. In the latter case there is no clear experimental data with which
to compare the result. The values of AEe.s,are also computed for 1,2- and 1,4-
naphthoquinone, and in all cases where comparison is possible there is qualitative
agreement between the calculations and observations. The spectral shifts observed
on dissolving diatomic molecules in solvents where the dominant solvent-solute
interaction is due to dispersion-type forces can be successfully predicted by a model
based on a new method for obtaining the potential function of liquids.14’ The
importance of vibronic interactions in molecules on the solvent shift of their
electronic spectra has been discussed, and an extension of the Longuet-Higgins
and Pople theory of the red shift of the electronic spectrum of a non-polar molecule
in a non-polar medium has been published. 1 5 ’
A review of the evaluation of the structural parameters of molecules in their
excited electronic states, which gives particular attention to the polydimensional
’
Franck-Condon method, has appeared. 5 2 A general equation has been obtained,
in the Hertzberg-Teller approximation, for the intensity distribution in the vibronic
spectra of polyatomic molecules, 5 3 and deviations from mirror symmetry in the
diffuse absorption and emission spectra of vapour-phase polyatomic molecules
have been discussed. 5 4
146
K. Wittel and S. P. McGlynn, Chem. Rev., 1977, 77, 745.
14’
I. Fischer-Hjalmars, A. Henriksson-Enflo, and C. Herrmann, Chem. Phys., 1977, 24, 167.
14’
I. Jano, C. R . Hebd. Seances Acad. Sci., 1965, 261, 103.
149
I . A. Vinokurov, S. Kh. Akopyan, and N. G. Bakhshiev, Vestn. Leningr. Univ.,Fiz.. Khim., 1978,114.
150
I. A. Ar’ev and G . G . Dyadyusha, Teor. Spektrosk., 1977, 25.
”’ A. M. Taleb and H. H. M. Al-Awath, Iraqi J . Sci., 1978, 19, 159.
15’
D. C. Moule, Vib. Spectra Struct., 1977, 6 , 227.
E. A. Gastilovich, K. V. Tskhai, and D. N. Shigorin, Dokl. Akad. Nauk SSSR, 1977, 236, 657.
154 S. 0. Mirumyants and Yu. S. Demchuk, Opt. Spektrosk., 1979, 46, 267.
26 Photochemistry
There have been a number of investigations recently of the effect of high pressures
on the fluorescence properties of molecules (vide infra). A timely paper has re-
examined the theoretical treatment of some earlier published experimental work on
the effect of high pressures (up to 8 GPa) on the absorption, and emission spectra of
anthracene, phenanthrene, and tetracene crystals and various solutions of these
molecules. 5 5 A model, due to Lin, in which the ground- and excited-state
potential functions take the general form given in equation (7), where p is the
I/= E, + : ( f w Z j Q Z j+ c j Q j p ) (7)
pressure, w2 is the force constant, Q a configuration co-ordinate, c a coupling

constant, and the sum is taken over j , the number of different normal modes, was
found to be compatible with the experimental data. The model should provide a
sound basis for the interpretation of high-pressure effects, particularly if it is
extended to include the effects of anharmonicity.
A simple kinetic model has been shown to be capable of reproducing in a
qualitative way the time-dependent photobleaching effects of solutions of a aye
molecule subject to a very intense picosecond light pulse. 15’ Experimental results
obtained for the saturable absorber DODCI were compared with those from a
simple model of a homogeneously broadened two-level system coupled by the three
fundamental radiative processes and a radiationless decay process. The only
parameters used in the model are molecular properties (rate constants and cross-
sections) measured under linear, low-intensity conditions. The model assumes that
the molecular energy levels are homogeneously broadened on a time-scale defined
by the interaction of the laser pulse with the medium and that there are no effects
arising from optical coherence. The model can be extended to include the effects of
broadband absorption and emission, excited-state absorption, photoisomer pro-
duction, and molecular rotation, when more quantitative agreement can be
expected. A number of discrepancies in the literature concerning the measurement
of basic photochemical parameters, such as quantum yields using laser flash
photolysis techniques, can be traced to a trivial non-linear effect.”’ When
undertaking investigations with this technique it is important to consider the effects
of both the excitation and analysing light beams on the system being studied.
Photoacoustic Spectroscopy.-There is a growing interest in the application of
photoacoustic (optoacoustic) measurements, and the related calorimetric and
thermal-lensing techniques, to topics of interest to photochemists and spectro-
scopists. This follows a number of notable papers reported in my previous review
(see ‘Photochemistry’,Volume 9, Part I, Chapter 1). The techniques combine a very
high sensitivity with the discrimination of optical absorption.
A general account of the optoacoustic effect has appeared; it includes an analysis
of the signal at the detector, following excitation of a generalized two-level
system.lS9The review also discusses the design of optoacoustic cells and the
155 R. C. Tompkins, J . Chem. Phys., 1978, 69, 579.

156 S. H. Lin, J . Chem. Phys., 1973, 59, 4458.
15’ G. L. Olson, K. S. Greve, and G. E. Busch, J . Chem. Phys., 1978,68, 1474.
15* C. R. Goldschmidt, Proc. SOC.Photo-Opt. instrum. Eng., 1977, 99, 252.
Is9 M. J. Colles, N. R. Geddes, and E. Mehdizadeh, Contemp. Phys., 1979, 20, 1 1 .
technique's application to the detection of pollutants, reactive intermediates, and
weak absorbers, to the measurement of relaxation times, and to problems in
photophysics such as the onset of dissociation in a spectral band and the
spectroscopy of solids. The results of thermal-lensing spectroscopy in condensed-
phase systems has also been reviewed with particular reference to the remarkable
experiments in which vibrational overtones in the visible region were measured. 160
The use of calorimetric techniques to measure various parameters of excited states
has also been discussed, and this includes the description of a number of simple
calorimeters which can be used for gaseous-, liquid-, or solid-phase systems. 1 6 1
A resonant optoacoustic cell for excited-state spectroscopy that has a Q of
1800 and can detect levels of SF, as low as 1 part in 10" has recently been
'
described. 6 2 Another significant development with respect to instrumentation is
the introduction of piezoelectric transducers for condensed-phase studies in the
place of microphones. The technique is greatly simplified because of the good
acoustic impedance match between detector and sample and this is illustrated both
in a recent study of Nd : glass laser material and in the first reports of pulsed
optoacoustic spectroscopy in liquids. 164 The use of the photoacoustic effect in
water as the basis for a pulsed laser energy monitor has also been demonstrated.
The study was able to establish a linear relation between the photoacoustic signal
and the pulse energy from Nd : YAG lasers operating in either a nanosecond or a
picosecond pulsed mode.
A generalized theory of the photoacoustic effect has been developed which
includes the contribution from the mechanical vibration of the sample. 166 The
results take a relatively simple algebraic form. Following an earlier proposal by the
authors,'67 the paper also describes an experiment, and its analysis, to obtain
absolute absorption coefficients by measuring a photoacoustic signal as a function
of the modulation frequency. The system chosen was a solution of the Na salt of
Phenol Red, and the new technique gave a result in good agreement with that found
from conventional absorption spectrophotometry. Similarly good agreement with
conventional methods was obtained in a study of dichroism in strongly absorbing
samples. 16*
An interesting paper has presented an analysis of the time dependence of the
pressure in an optoacoustic cell following the absorption of a pulse of radiation. '69
A simple two-state model is developed which, when applied to the case of excitation
to the lowest triplet level of a polyatomic molecule, shows that the measurement of
the time evolution of the pressure leads to the separate evaluation of the radiative
A. C. Albrecht in 'Advances in Laser Chemistry', ed. A. Zewail (Springer Series in Chemical Physics),
Springer-Verlag, Berlin, 1978, Vol. 3, p. 235.
16'
J . B. Callis, Nat. Bur. Stand. ( U S . ) ,Spec. Publ.. 1977, 466,25.
E. Nodov, Appl. Opt., 1978, 17, 1110.
M. M. Farrow, R. K. Burnham, M. Auzanneau, S. L. Olsen, N . Purdie, and E. M. Eyring, Appl. Opt.,
1978, 17, 1093.
164 C. K. N. Patel and A. C. Tam in 'Laser Spectroscopy IV', ed. H. Walther and K. W. Rother, Springer-
Verlag, Berlin, 1979, p. 646.
165 P. Sladky, R. Danieluis, V. Sirutkaitis, and M. Boudys, Czech. J . Phys., 1977, B27, 1075.
16' F. A. McDonald and G. C. Wetsel, jun., J . Appl. Phys., 1978, 49, 2313.
G. C. Wetsel, jun. and F. A. McDonald, Appl. Phys. Lett., 1977, 30,252.
D. Fournier, A. C. Boccara, and J. Badoz, Appl. Phys. Lett., 1978, 32, 640.
J. Wrobel and M. Vala, Chem. Phys.. 1978, 33, 93.
28 Photochemistry
and non-radiative decay constants. If a separate measurement of the phosphores-
cence quantum yield is available the results taken together will yield a value for the
intersystem-crossing (triplet) quantum yield.
A study of the trace analysis of permanganate ion in aqueous solution has shown
that !aser-induced photoacoustic spectroscopy can detect MnO,- concentrations
as low as 5 x 10- 'moldm- 3, which is a factor of 60 lower than that found by
conventional colorimetric analysis. 7 0 Aspin-flip Raman (SFR) laser was used in a
high-resolution optoacoustic study of the vibrational-rotational transitions in the
2n1,2,2 ~ 3 , 2excited states of NO.i71The study also presented some preliminary
results of optoacoustic Zeeman spectral measurements. Such measurements are
practical because the high sensitivity of the technique makes it possible to use short
(1 cm) path-length cells which can be placed inside the cavity of a superconducting
magnet. The high-resolution spectra of CH,, C2H4, and C,H, have been measured
in the Zeeman displacement region of a He-Ne laser operating at 3.39 pn.1 7 2
In thermal-lensing experiments the heat deposited in the path of a laser beam
passing through an absorbing medium alters the refractive index in such a way as to
produce a divergent lens. The consequent loss of intensity measured by a detector
on the laser-beam axis but downfield from the absorbing medium has proved to be
an extremely sensitive measure of absorption. It has been used to measure ultra-
weak absorptions and as a probe in energy-transfer experiments. In connection
with the latter, recent measurements of the thermal conductivity of C2H4 and
C2H,Cl in an apparatus suitable for energy-transfer measurements gave values
which were in poor agreement with literature values until a relaxation model based
on the laser-beam diameter was introduced.173The discrepancy was traced to
complex Fresnel diffraction patterns produced by the iris in front of the absorption
cell. An example of the use of thermal lensing in energy-transfer studies is in a paper
on the vibrational energy flow in CD3H and its mixtures with SF,, SiF,, and
CF,.174
The important application of the optocoustic method to the measurement of
fluorescence quantum yields will be reported in a later section.
Single-photon Absorption Spectra.-Coverage under this heading is necessarily very
restricted because of the large number of publications that qualify for consider-
ation. Systems of general interest to photochemists have been selected, and, such
that it is, any emphasis is given to excited-state absorption spectra, particularly
triplet-triplet absorption spectra
An interesting review article has considered the impact of dye laser measurement
techniques on the spectroscopy of small molecules. 7 5 The new developments in the
techniques of absorption and emission spectroscopy are discussed and include
those which go beyond the simple measurement of the energies of the eigenstates,
i.e. lifetimes, Lande factors, chemical shifts, collision cross-section, etc. A simple
model for the solvated electron which uses a rectangular potential well with
'lo S. Oda, T. Sawada, and H. Kamada, Bunseki Kuguku, 1978, 27, 269.
C. K. N. Patel, R. J. Kerl, and E. G. Burkhardt, Phys. Rev. Lett., 1977, 38, 1204.
A. B. Antipov and V. A. Sapozhnikova, Zh. Prikl. Spektrosk., 1978, 28, 636.
173
R . T. Bailey, F. R. Cruikshank, D. Pugh, and W. Johnstone, Chem. Phys. Letr., 1978, 59, 324.
174 W. S. Drozdoski, R. D. Bates, jun., and D . R. Siebert, J . Chem. Phys., 1978, 69, 863.
J. C. Lehmann, Rep. Prog. Phys., 1978, 41, 1609.
spherical geometry has been used to interpret its absorption spectrum in a variety of
solvent systems including simple alcohols. 76 Two experimental moments of the
absorption spectrum are used to calculate the two parameters of the model, the well
depth, and its radius, and these in turn are used to calculate a third moment which is
compared with the experimental third moment. The parameters obtained indicated
that for the solvent systems studied the optical transition is bound-free. It was also
shown that the model is compatible with short-range interactions involving only the
first solvation layer. The effect of pressures up to 2.2kbar on the absorption
spectrum of the solvated electron in water and several alcohols has shown that the
relative increase in jmaX with pressure is greater in the alcohols than in water and
that the shifts correlate with increases in the densities of the liquids. 177 The same
authors have also measured the absorption spectra of solvated electrons in water,
several alcohols, and tetrahydrofuran over an extended wavelength range and then
empirically resolved the spectra into two Gaussian bands and a continuum tail. 17*
The alchols, except for t-butyl alcohol, were found to have very similar components
with respect to their half-width and oscillator strengths.
The results of an extensive series of measurements of the charge-transfer-to-
solvent (CTTS) spectrum of the chloride ion in a number of solvents have been
published. 17' The more easily obtained equivalent data for the bromide and iodide
ions were already available in the literature. The chloride-ion spectra are broad and
show none of the doublet splitting which is characteristic for the other halide ions.
For comparison the results for the three ions are summarized in Figure 8, which is a
possible potential-energy diagram for the halide-ion CTTS band spectra. As can be
seen from the figure there are two types of bands present: firstly a low-energy set of
bands, A , B, C , etc., which show the atom doublet 2Pstate splitting to give A ,-A 2,
p 601 E-
D
X
c
g
I
55-
2
Q)
n
5 50.
C
Q,
>
45-
40 -
iodide bromide chloride
Figure 8 Relationship between energy levels for the halides in propionitrile at 298 K
(Reproduced with permission from J . Chem. SOC.,Faraday Trans. I, 1978, 74, 1776)
176
M. De Backer, J.-P. Lelieur, and G. Lepoutre, J . Phys. Chem., 1978,82, 2701.
177
F.-Y. Jou and G. R. Freeman, J . Phys. Chem., 1977, 81, 909.
''13
F.-Y. Jou and G. R . Freeman, Can. J . Chem., 1979, 57, 591.
179
M . F. FOX,B. E. Barker, and E. Hayon, J . Chem. SOC.,Faraday Trans. I , 1978,14, 1776.
30 Photochemistry
B,-B,, etc., and secondly bands D and E which exhibit behaviour that in some
respects is different from that of the first group. The first group has previously been
attributed to s-type electron states, i.e. 1s for the A band, 2s for the B band, etc. The
present authors support the suggestion that the D and E bands correspond to a d-
type solvated electron state. In the theory of CTTS spectra due to Franck and
Platzman (1954) the effect of the solvent on the potential-energy function of the
solvated electron was introduced via the solvent dielectric constant. A new
treatment has been published in which the effect of the solvent dipoles is
included. '8o This results in significantly lower calculated values for the electron-
binding energy. A configuration-mixing model has been very successful in
accounting for the colours and luminescence properties of post-transition-metal
salts in which neither the anion nor the cation is coloured. "' The model uses locally
excited and charge-transfer configurations that, despite building into the model a
number of limitations, d o make it possible to use available experimental data for the
locally excited states of the anion and cation and for the charge-transfer states of the
anion<ation system. The interesting results show that the colour of post-
transition-metal salts, e.g. AgNO,, can be attributed to spin-orbit mixing with, and
intensity borrowing from, charge-transfer transitions of anion-to-metal type. In the
case of light non-transition-metal salts, e.g. NaNO,, the intensity is borrowed from
local excitations. The five generic configuration wave functions are illustrated in
Figure 9, and the transition responsible for the colour is +o + ~ A * .
-
A } +RCT
Reverse
charge transfer
I) +cT Charge transfer

I I
a
-
=
en
0
3.
I Locally excited
u }Q
7 locally excited
anion
I
ANION- METAL+
A- M+
Figure 9 An illustration of thefive generic configuration wave functions. The energy scale is
suggestive. The salt is designated A - M for convenience. The upper MO of any pair is the
+
LUMO and the lower is the HOMO

(Reproduced with permission from J . Am. Chem. Soc., 1979, 100, 1728)
K. Tennakone and R. H . Wijenayake, Natl. Sci. Counc. Sri Lanka, 1977,5, 157.
T. P. Carsey and S. P. McGlynn, J . Am. Chem. Soc., 1979, 101, 1728.
A major investigation of the 'B2" t ' A lg absorption system of benzene vapour
'
has been published. The last major analysis of this band, which is of considerable
theoretical interest as a vibronically induced electric-dipole transition, was that of
Ingold and co-workers in 1946. Since then the work of Callomon, Dunn, and Mills
(1966) on the consequences of vibrational angular momentum and recent single-
vibronic-level (SVL) fluorescence studies have provided the basis for a further
analysis of the spectrum. The present work represents a major advance in the
understanding of the 'BZut ' A lg system, as is evidenced by the fact that over 90%
of the intensity is assigned. To enable them to progress with the analysis the authors
developed a general treatment of vibrational angular momentum in benzene which
makes it possible to predict the rotational-band contour of any vibronic-
component transition and which, they argue, can be applied, after minor
modifications, to determine the extent of vibrational angular momentum effects in
the spectra of other large polyatomic molecules. The vibronically active modes ( v4,
',
v5, v g , v7, vg, vl0, v1 v16, ~ 1 7 and
) the general pattern ofintensities were found to be
similar to those observed in SVL studies. The presence of a number of small and
unidentified perturbations in vibronic levels of 1B2u were seen as variations in the
separation of progression members. The role of the Duschinsky effect, i.e. mode
mixing, on the vibronic intensities in the one- and two-photon spectra of the
' B l u t-' A lg transition in benzene has been considered. 83 The analysis which uses
excited-state normal co-ordinates and not ground-state normal co-ordinates
throughout shows that the Duschinsky effect leads to large asymmetries in the
intensities of coupling modes in the same symmetry species. The vibronic structure
in Jahn-Teller active states of benzene has been analysed. lS4Ithas been attributed
to two Rydberg systems.
The vibronic intensities in the electronic transitions of naphthalene, particularly
for the lowest-energy singlet transition ' B , +- 'Ag,have been calculated using '
a method which has also recently been used for a similar study of benzene. lS6 If
%(g)represents the electronic-transition moment for the nuclei fixed in configur-
ation Q and @ ;) = (i@) IKNQ)), where i@) ) and Ng)) are electronic
I
wavefunctions for the initial and final states and i i s the electric-dipole operator,
then the method involves calculating the l i ( 0 ) ) at a series of selected nuclear
configurations, e.g. along a chosen normal co-ordinate, and using these to calculate
$0) at each of the chosen configurations. The %(Q)results in vibronic intensities
following integration over the vibrational wavefunctions. The success of the
method depends on the quality of the wavefunctions, and in the present study the
CNDO/S CI method was used to calculate them. For one-photon spectra
reasonable agreement was found between experiment and calculation.
A surprising result has been found from a theoretical analysis of bacteriochloro-
phyll a protein's 800nm absorption band and its c.d. spectra.lS7There are pro-
nounced exciton effects in the spectrum of this complex, but its structure is known
G. H. Atkinson and C. S. Parrnenter, J . Mol. Spectrosc., 1978,73,20;ibid., 1978,73,31;ibid; 1978,73,
52.
la'
F. Metz, M . J . Robey, E. W. Schlag, and F. Dorr, Chem. Phys. Lett., 1977, 51, 8.
J . Hah, B. Katz, and B. Scharf. Chem. Phys. Lett., 1977, 52, 92.
185
M. J. Robey, I . G. Ross, R. V. Southwood-Jones, and S. J. Strickler, Chem. Phys.. 1977, 23, 207.
L. Ziegler and A. C. Albrecht, J . Chem. Phys., 1974, 60,3558.
IS7
R . M. Pearlstein and R . P. Hemenger, Proc. Natl. Acad. Sci. U.S.A., 1978, 75, 4920.
32 Photochemistry
and calculations of the spectrum based on this structure were found to be
compatible with the usual assignment of the lowest-energy band as Qy (y-
polarized). Good agreement was obtained only if the transition was x-polarized
rather than y-polarized. This may indicate a systematic error in the structural
analysis or a strong environmental perturbation which lowers the energy of an x-
polarized state to below that of Qy.
The cyanocarbene radical HCCN has been produced by photolysis of N,CHCN
'''
in a low-temperature argon matrix. The radical has a linear allenic configuration
in the ground electronic state, where it is a triplet. A structured transition in the U.V.
region has been attributed to a 3Z-3Ctransition involving x-n* excitation because
of its similarities to the corresponding transition in the isoelectronic NCN free
radical. Triplet-triplet (T-T) absorption spectra of simple substituted benzenes in
the gas phase have been measured in the relatively inaccessible region from
'
220-250 nm by modulated absorption spectrophotometry. 89 The first-order non-
radiative and bimolecular quenching rate constants of the triplets were obtained
from studies at different pressures, and an interesting observation was the
remarkable decrease in the non-radiative decay constant upon fluorination and
trifluoromethylation. Related studies of these systems were also undertaken by
laser flash photolysis. 190 A marked broadening of the T-T absorption spectra of a
number of aromatic molecules has been observed in low-temperature matrices
formed by aromatic solvents, e.g. toluene, as compared with those in aliphatic
solvents, e.g. ethanol.19' A strong dependence of the broadening on the triplet
energy of the solute has been interpreted as evidence for a strong resonance
exchange interaction between the triplet states of the solvent and solute.
A very interesting tandem laser pulse absorption experiment on naphthalene in
the vapour phase has clearly shown the time evolution of the 3B,, t 'B,,, triplet
absorption spectrum from a broad, structured, and unrelaxed form to a narrow
featureless band familiar from previous studies of naphthalene. '92 In the experi-
ment a short laser pulse initiates triplet formation and the absorption is probed at
well defined delay times by a second scanning pulsed laser. The T-T absorption
'
spectra of 1,2- and 1,8-dinitronaphthalene, 93 4-nitro-ar-naphthylamine, 194 and 3-
'
nitropyrene 9 5 have been observed in laser flash photolysis experiments. The
electronic transition energies for the T-T absorption and the phosphorescence of
1,l'-binaphthyl calculated by the PPP CI method were in agreement with
'
experimental observations, 96 and the polarizations of the T-T absorption bands
of diphenylacetylene have been determined from measurements in stretched
polymer films at liquid-nitrogen temperatures. 1 9 7 The rates of the internal
conversion and intersystem-crossing decay routes of the first excited singlet of the
fluorescent aza-aromatic acridine have been obtained by measurement of the rate of
la' A. Dendramis and G . E. Leroi, J . Chem. Phys., 1977, 66,4334.
M . E. Sime and D . Phillips, Chem. Phys. Lett.. 1978, 56, 138.
I9O R. Bonneau, M, E. Sime, and D . Phillips, J . Phorochem., 1978, 8, 239.
19' M. F. Alfimov, V. 1. Gerko, L. S. Popov, and V . F. Razumov, Chem. Phys. L e f t . , 1977. 50, 398.
19* H. Schriider, H. J . Neusser, and E. W. Schlag, Chem. Phys. Letr., 1978, 54, 4.
193 C. Capellos and K . Suryanarayanan, i n [ . J . Chem. Kinet., 1977, 9, 399.
194 C. Capellos and F. Lang, Int. J . Chem. Kinet., 1971, 9, 409.
'95 R . Scheerer and A, Henglein, Ber. Bunsenges. Phys. Chem., 1977, 81, 1234.
'96 J. Suehnel, K. Gustav, and U . P. Wild, Z . Chem., 1978, 18, 387.
19' T. Hoshi, K. Ota, J . Yoshino, K . Murofushi, and Y . Tanizaki, Chem. Lett., 1977, 357.
T-T absorption growth on a picosecond time-scale. 19' The results were interpreted
to give an n.11C assignment to the first excited singlet state and to indicate the
presence of an important internal conversion process.
Triplet states of N-methyl-2-N-phenylamino-6-naphthalenesulphonate (1 ; N-
methyl ANS) and its C-protonated form, the N-methylbetaine of 6-sulfonato-3/3-
tetralenone N-phenylimine (2), have been produced by laser flash photolysis and
shown not to interconvert either in glycerol or in dioxan-water at 25 "C.199 This
- \ /
fJYJ"0
\
H H
/
yH3
/
03s 03s
(1) (2)
result supports earlier work on the multiple fluorescences of (1) observed in

glycerol, which indicate that the protonated form is produced from a vibrationally
excited ground state. The parent molecule ANS is widely used as a non-covalent
non-specific probe of biological environments, e.g. protein binding sites. The
transient absorptions observed on laser excitation of 1-acetylcyclohexene have been
attributed to the strained trans form and an orthogonal triplet state.200The T-T
absorption spectra of the organic dyes Rhodamine 6G, NN-diethylrhodamine,
and Rhodamine B have been measured in a study which is clearly relevant to the
function of these dyes in the active media of dye lasers. 2 0 1 The study also obtained
values for the intersystem-crossing yields of 0.002, 0.005, and 0.006, respectively.
A laser flash photolysis of 1 1-cis-retinal has shown that the resulting transient
absorption is due to the triplet states of both the 1 1-cis and all-trans triplet states. '02
The data were treated to give the separate triplet absorption spectra of theisomers
in the 3 0 G 5 0 0 n m region and furthermore to support a mechanism for photo-
isomerization that involves an unrelaxed triplet state. A laser flash photolysis study
of the effect of 8a-substitution on the yield and decay rate of flavin triplet state
indicates that an a-amino group may be an effective intra- and/or inter-molecular
triplet quencher. 203 Acetylation of the a-amino groups and the ribityl side chain of
8a-histidylriboflavin was found to double the triplet yield and halve its decay rate. A
valuable study has characterized the triplet states from a number of carbonyl-
containing polyenes by measuring or estimating their absorption spectra, lifetimes,
extinction coefficients, production quantum efficiencies, and lowest energy
levels.204 The results are summarized in Tables 2a and 2b. A number of correlations
were found, some of which are paralleled by the behaviour of the corresponding
singlet states, and the results were useful in a discussion of the character of the
lowest states, i.e. whether an (n,n*) or a (n,.11C)label is appropriate. The triplet states
19' V. Sundstrom, P. M . Rentzepis, and E. C. Lim, J . Chem. Phjs., 1977, 66, 4287.
lYy H. Dodnik, E. M . Kosower, M. Ottolenghi, and N. Orbach, Chem. Phys. Lett., 1977, 49, 174.
zoo R . Bonneau and P. Fornier de Violet, C. R . Acud. Sci. Ser. C , 1977, 284,631.
2 0 1 V. E. Korobov and A. K . Chibisov, J . Phorochem.. 1978, 9, 411.
'02
B. Veryat, S. G . Davis, M . Yoshida, and K . Weiss, J . Am. Chem. SOC.,1978, 100, 3283.
*03 D . E. Edmondson, F. Riuuto, and G. Tollin, Photochem. Photobiol., 1977, 25, 445.
'04 R. S. Becker, R. V. Bensasson, J. Lafferty, T. G . Truscott, and E. J . Land, J . Chem. SOC.,Furuduy
Trans. 2, 1978, 74, 2246.
34 Photochemistry
Table 2s Triplet-triplet extinction coeficients and quantum eficiencies of
production of the lowest triplet (aT,) for carbonylpolyenes in hexane"
(ieXc = 265nm)
Ex tinction coeflcien t
Carbonylpolyenes A,,,/nm E T,/dm3 mol - cm - @TI
/?-Ionone (C, J 330 85 300 0.10
8-Ionylidene acetaldehyde (C, 5 ) 385 38 500 0.42
trans-Retinal (C20) 445 78 000 0.40
/?-Apo-l4carotenal (C22) 470 127 000 0.41
B-Apo-8'-carotenal (C30) 520 223 000 0.003
Torularhodinaldehyde (C40) 580 363 000 0.001
a ~ T and
, QT, are considered to be correct to f 15%.
Table 2b Triplet energy levels (ETI)

andfirst-order rate constants ( k , ) f 15% for
the triplet-state decay
ETl/kJmol-' 10-6k,/s-1
/?-Ionone (C13) 207 f 12 6.3
B-Ionylidene acetaldehyde (C 5) 188.1 & 12 10
Retinal (C20) 158.8 0.1
/?-Apo-l4carotenal (C,,) 1484(121)b 0.2
B-Apo-8'-carotenal (C30) 1224 ( s 7 ) b 0.4
Torularhodinaldehyde (C4,,) 94" (63)b 0.2
'Values predicted by extrapolation of the straight-line plot of l/ET, against number of double bonds,
using the present data for C I 3 ,C, 5, and C , , carbonyl polyenes. 'Values predicted by extrapolation of the
straight-line plot of l/&, against number of double bonds, using Evans' data. (D. F. Evans, J. Chem. SOC.,
1961, 2566)
of copper and metal-free phthalocyanines have been characterized in a laser

photolysis study. 2 0 5
Two-photon Absorption Spectra.-There has been a marked growth in the number
of papers dealing with the theory of two-photon processes since my last review in
this title series. A generalized theory of two-photon transient phenomena for the
case where two radiation fields interact with an N +
2 level quantum system has
been developed.' 0 6 The system treated is shown in Figure 10a, together with that
(a) (b)
Figure 10 Two-photon processes for an N + 2 level system, showing (a) two-photon
absorption and (b) the Raman process
(Reproduced with permission from Phys. Rep., 1978, 43,455)
205 J. McVie, R. S. Sinclair, and T. G. Truscott, J. Chem. SOC.,Faraday Trans. 2, 1978, 74, 1870.
*06 A Schenzle and R. G. Brewer, Phys. Rep., 1978, 43, 456.
for the related Raman process, Figure lob. The N intermediate transitions are
regarded as far off resonance, and the systems are assumed to be homogeneously
broadened. Although the general problem cannot be solved analytically an effective
Hamiltonian is derived which is equivalent to a two-level quantum problem, and
the application of perturbation theory leads then to a continued fraction expansion,
the leading terms of which agree with earlier treatments. As an example of the
application of new non-perturbative solutions to the problem, which unlike
perturbative solutions can account for intensity-dependent dephasing, the authors
consider the Raman beat effect in which a transient forward scattering is observed
from a system represented by Figure lob, in which 1 and 2 are initially degenerate,
but which is subjected to a Stark pulse that lifts the degeneracy. An important paper
has considered the theory of two-photon absorption by gas-phase molecules. 207 A
new theory is presented which includes the effects of rotation within the rigid rotor
approximation and which leads to general formulae for the transition probabilities,
W , between rovibronic states. The latter contain three terms which, as in Raman
theory, are derived from the isotropic and the antisymmetric and symmetric
anisotropic tensor components. For the case of a symmetric rotor each of these
terms splits into three factors: W = C&&, + C , M , R , + C2M,R2,where the
C j are geometrical factors which reflect the initial polarization of the incoming
photon in relation to the rotating molecules, the M,-are molecular factors arising
from the two-photon absorption tensor, and the R,- are rotational factors which
describe the projection of the tensor on the rotational states. The calculations are
more difficult for the asymmetric rotor case as the projection of the total angular
momentum along the top axis is no longer conserved. Thus the factorization into R,-
and Myis no longer possible, but the resulting expression still contains three terms
each with the same geometrical factor as in the corresponding term in the above
equation. An important feature of the new theory is that it accounts for
experimental observations of different polarization behaviour for different rota-
tional branches within the same vibronic band. This effect does not occur in either
one-photon absorption spectroscopy or in the two-photon spectra of non-rotating
molecules, but the above expression for W shows that it is a quite general
phenomenon requiring only two non-zero terms in the equation. The paper
concludes by presenting model calculations of the band contour of a two-photon
transition in the asymmetric rotor naphthalene, a result of which is shown in Figure
11, and it is emphasized that such calculations are as straightforward as those for
one-photon band contours.
A discussion of two-photon absorption in crystals shows that it is possible, quite
generally, to determine the symmetry properties of the excited states if it is possible
to have one or both of the beams circularly polarized. 2 0 8 The theoretical treatment
factorizes the absorption coefficient into dynamical factors containing matrix
elements of the momentum operator and geometrical factors which depend on the
polarization directions of linearly polarized light and on the propagation vectors of
circularly polarized light. The geometrical factors for several point groups are
presented in Tables la and lb.
207 F. Metz, W. E. Howard, L. Wunsch, H. J. Neusser, and E. W. Schlag, Proc. R . SOC.London, Ser. A ,
1978, 343, 381.
2n8 E. Doni, R . Girlanda, and G. Pastori Parravicini, Phys. Status Solidi B, 1978, 88, 773.
36 Photochemistry
High-resolution two-photon absorption (TPA) spectroscopic studies, usually
under Doppler-free conditions, are carried out by detecting the fluorescence
emitted by the two-photon excited state, the absorption itself usually being too
31
I I I
0 7.5 0 -25 -15.0
Relative excitation energy / c m - l
Figure 11 Computed band contour of an as two-photon transition in naphthalene, h, at 300K
for two linear photons wirh values M,, = 0, M y , = 0.1, and M,, = 0.9
(Reproduced with permission from Proc. R . SOC.London, Ser. A , 1978, 363, 381)
small to detect. A theoretical treatment of two-photon excited fluorescence(TPEF)

has recently been published; it considers the case of a symmetric top under collision-
free conditions with an unpolarized ground state. 209 The treatment uses a density-
matrix formalism which has proven to be useful in discussing polarization effects in,
for example, optical pumping experiments. The TPEF intensity is given by the trace
of a product between the excited-state density matrix p, and a detection operator,
and the resulting expressions for the AK # 0 case can be transformed into a very
condensed form which contains all the polarization and angular-momentum
dependencies. For the case where AK = 0 a quantum interference term appears in
the TPEF intensity expression. The same authors have also published a detailed
analysis of rotational line strengths and selection rules of TPA for symmetric top
molecules in the gas The complementary properties of a complete TPA
polarization study and a high-resolution study for gas-phase molecules are
discussed, and it is shown that, where possible, high-resolution studies would be
more appropriate for making state assignments in molecules with C3h, D3h,C3,C,,,
D6, C6h, and D6,,point symmetry. It is also shown that for a molecule with no low-
lying resonance-enhanced intermediate state a complete polarization study is
209 K . M . Chen and E. S. Yeung, J . Chem. Phys., 1979, 70, 1312
"O K . M. Chen and E. S. Yeung, J . Chem. Phys.. 1978,69,43.
possible using identical-frequency TPA with both parallel linearly polarized and
same-sense circularly polarized photons. The paper also identifies a general
selection rule for TPA in which the initial and final states have identical overall
rovibronic symmetry. The Mselection rules derived for D6,,molecules are shown in
Table 3.
Table 3 AK selection rules and excited-state symmetry of a D,, ndecule
Vibronic Identical TPA Non-identical TPA
symmetry' <$$,An> <no,
1-,
A2g(blu) Forbidden AK=o
( P , Q , R branches
only)
Alg(b2u) AK = 0 AK = 0
(Anomalous polarization
ratios for Q branch)
E2gh u ) bK=+2 A K = +2
rmncrr)mcnn) = 2/31
Elg(e2u) AK=+l A K = +1
t2Jlm(W/Nn
(V=2/31 (New contributions
to P , Q,and R
branches)
'The parentheses indicate the vibrational modes of a B,, excited electronic state.
A new quantum statistical theory of optical phenomena, which uses a density-

matrix formulation, can be applied to both steady and transient states and to both
'
resonance and off-resonance regions. " The relation between a recent two-photon
vector model and recent models of multiphoton coherent excitation has been
discussed, 2 1 and a general non-perturbative theoretical analysis of two-photon
magneto-optic effects such as polarization rotation and circular dichroism has been
presenteda213The latter predicts a new effect which is the optical analogue of the
Hanle effect. Time-dependent perturbation theory has been used to calculate the
probability amplitudes for two-photon absorption, and the resulting expressions
were applied to rare-earth and actinide ion systems.214A theory of two-photon
absorption from a broad-band steady-state radiation field has predicted that for the
case of coherent excitation the transition probability is larger than that for the
'
incoherent excitation case. A density-matrix method has been used to study the
interaction of a three-level system with two monochromatic a-polarized light
beams. 16Theapproximation to fourth order describes the double-quantum Hanle
effect, mentioned above, and the influence on the two-photon transition probability
of the Hanle effect and saturation phenomena. The Doppler-free photon absorp-
tion by a three-level system with a near-resonant intermediate state has been
''
considered. * The resulting analytical solution obtained within the rotating-wave
211 S. H. Lin and H. Eyring, Proc. Natl. Acad. Sci. U.S.A., 1977, 74, 3105.
'I2 M. M. T. Loy and D. Grischkowsky, Opt. Commun., 1977, 21;379.
213 V. P. Kaflandjian and L. Klein, Phys. Lett. A , 1977, 62, 317.
J . B. Gruber, E. D. Larson, D. N. Olsen, and T. R. Stoner, Proc. N . D. Acad. Sci., 1978, 31, 218.
215 H. Sekiya, S. Tsunekawa, K. Nishikawa, and A. Sado, Sci. Rep. Kanazawa Univ., 1977, 22, 21.
'I6 M. Kolwas, J . Phys. B, 1977, 10, 583.
217 D. P. Hodgkinson and J. S. Briggs, Opt. Commun., 1977, 22, 45.
38 Photochemistry
approximation shows, amongst other things, conditions where an effective
saturation between the first and third levels may be achieved, with the intermediate
level acting as a virtual state only. The new features of atomic absorption revealed
by the use of coherent light sources have been discussed, and a mechanism for
determining the phase of Doppler-free coherent atomic absorption amplitudes was
identified. ”*
A quantum-mechanical calculation has demonstrated the high probability of
two-photon absorption by light emitted in a two-photon spontaneous decay
process relative to light from ordinary sources, a result which one expects
intuitively. ” A theory of the absorption lineshape on two-photon excitation of a
two-level system has confirmed an experimental observation that negative absorp-
tion, i.e. amplification, without a population inversion can be achieved when the
probability of two-photon excitation is sufficiently high. ’O The observations lead
to a method to generate the third-harmonic frequencies of lasers, and model
calculations are performed for the tripling of the 778.4 nm line of sodium vapour.
The limitations of a perturbation theory approach to the problem of the coherent
propagation of a circularly polarized pulse that is two-photon quasi-resonant with
a medium of multilevel atoms are exposed in a paper which uses multiphoton
coherent excitation theory in the adiabatic following limit ’”
(see reference 212).
The resonance fluorescence excitation spectrum of a two-level atom in a radiation
field whose frequency corresponds to nearly half the level separation has been
shown to consist of four Lorentzian lines: a central line peaked near the two-photon
resonance with a lower- and a higher-frequency sideband and the one-photon
frequency mode. ”’
An interesting paper has examined both experimentally and
theoretically the dependence of the degree of polarization of luminescence on the
frequency difference between the two photons absorbed in the two-photon
excitation process. 2 2 3 The effect arises mainly from the antisymmetric part of the
two-photon transition tensor, and it was demonstrated in glycerin solutions
of 1,3,5-triphenylpyrazoline, 1-phenyl-3-[acenaphthyl( 5)]-5-[fluorenyl(2)-]-A2-
pyrazoline, 4-formylamino-N-methylphthalimide, and 3-aminophthalimide.
A number of general and review articles on two-photon spectroscopy have been
published. A useful general account of the basic physics of two-photon absorption
is contained in an article on two-photon molecular spectroscopy in liquids and
gases. 2 2 4 A full quantum-mechanical treatment for gaseous symmetric-rotor
systems is presented that explicitly contains rotational effects (see reference 207).
Unlike the situation in condensed media it is not possible to predict correctly the
two-photon behaviour of gaseous systems by averaging the single-molecule result
against an orientational distribution function. The theoretical treatment is based on
an irreducible representation of the two-photon transition tensor which may be
’I8 M. C. Li, Nuovo Cimento SOC.Ital. Fis. B, 1977, 39, 165.

’‘’
’‘O
I. V. Solokov, Zh. Eksp. Teor. Fiz.. 1977, 72, 1687.
V. A . Khodovoi and N . A. Chigir, Zh. Eskp. Teor. Fiz., 1978, 74, 67.
”I F. H . M. Faisal, J . Phys. B, 1977, 10, 2003.
”’ C. Mavroyannis, Opt. Commun., 1978, 26, 453.
223 V. A. Gaisenok, I. A. Dudarev, M. Kadum, A. P. Klishchenko, and A. M. Sarzhevskii, Dokl. Akad.
Nauk SSSR, 1979, 23, 35.
224 W. M. McClain and R. A. Harris in ‘Excited States’, ed. E. C. Lim, Academic Press, London, 1977,
V O l . 3, p. 1.
derived from its usual Cartesian representation. The use of tensors in irreducible
representation is illustrated by a helpful discussion of two-photon band contours in
benzene. High-resolution Doppler-free multiphoton spectroscopy has been re-
~ i e ~ e das, has ~ ~its~ application
, ~ ~ ~ to the study of molecular electronic
transition^.^^ A review of the multiphoton and multistep vibrational laser
spectroscopy of molecules has also appeared.228
The existing experimental techniques of two-photon spectroscopy have been
reviewed 2 2 9 and a number of new techniques reported. A two-photon spectrometer
using two independently tuned flashlamp-pumped dye lasers has been described,230
as has a new technique for measuring the TPA spectrum of molecules, in which the
system is situated in the cavity of a broad-band probe laser and is subjected to a
narrow second-pump photon injected into the cavity from another laser. 2 3 1 An
accurate method for TPA measurements has been developed which involves
measuring the time-resolved difference between two optical signals,2 3 2 and TPA
measurements in solids, using calorimetric methods, have been reported. 233 An
efficient optical system for the detection of TPEF in liquids has made it possible to
perform experiments with very low-power CW lasers,234 and a new on-line
technique for the measurement of picosecond-laser-pulse durations using TPEF
has been described. 235 A simple and accurate method to give reference wavelengths
for dye lasers has been developed; it involves the observation of Doppler-free two-
photon transitions to alkali-atom Rydberg levels. 236
The first measurements of Doppler-free two-photon linewidths obtained with a
simple coherent transient technique, namely two-photon optical-free-induction
decay, using a broad-band laser have been reported. 2 3 7 It was possible to measure
pressure-broadened linewidths of tens of MHz by using laser linewidths of several
GHz. A new method for the absolute determination of TPA coefficients by
comparison with known inverse-Raman cross-sections can also be applied to the
accurate determination of Raman cross-sections.2 3 8 Coherent Doppler-free TPA
experiments have been discussed,239 and an elegant demonstration of Ramsey’s
interference fringes in the profile of Doppler-free two-photon resonances has been
published. 240 In the latter paper two coherent time-delayed short pulses were used
to produce the fringes with a separation of 1/2T, which is much smaller than the
spectral width l / z of each of the pulses ( T is the pulse separation and z the pulse
225 B. Cagnac, A t . Phys.. 1977, 5 , 147.

G. Grynberg and B. Cagnac, Rep. Prog. Phys., 1977,40, 791.
”’
226
J. A. Gelbwachs and J. E. Wessel, Opt. Eng., 1977, 16, 197.
’” V. S. Letokhov, Comments At. Mol. Phys., 1978, 8, 39.
229 D. Frohlich and M. Sondergeld, J. Phys. E, 1977, 10, 761.
230 V. Sethuraman, G. J. Small, and E. S. Yeung, Rev. Sci. Inst., 1977, 48, 1436.
23L J. P. Reilly and J. H. Clark in ‘Advances in Laser Chemistry’ (Springer Ser. Chem. Phys.), Springer-
Verlag, Berlin, 1978, Vol. 3, p. 355.
232 W. Kleinsteuber and K. Ruehle, Exp. Tech. Phys., 1977, 25, 335.
233 M. Bass, E. W. Van Stryland, and A. F. Stewart. Appl. Phys. Lett., 1979, 34, 142.
234 C. Radzewicz, P. Glowczewski, and J. Krasinski, Appl. Phys., 1978, 17, 423.
235 J. Taboada and D. D. Venable, J. Appl. Phys., 1978,49, 5669.
236 S. A. Lee, J. Helmcke, J. L. Hall, and B. P. Stoicheff, Opt. Lett., 1978, 3, 141.
237 P. F. Liao, N. P. Economou, and R. R. Freeman, Phys. Rev. Lett., 1977, 39, 1473.
23n H. Lotem and C. B. De Araujo, Phys. Rev. B, 1977, 16, 1711.
239 M. C. Li, Phys. Rev. A , 1977, 16, 2480.
240 M. M. Salour, Appl; Phys., 1978, 15, 119.
40 Photochemistry
duration). The technique, which should be valuable in studies of ultra-high-
resolution laser spectroscopy, is also discussed in an article by the same author
which describes a number of new techniques and measurements in the ultra-high-
resolution two-photon spectroscopy of atomic and molecular vapours. 241
No attempt to report on the numerous experimental studies of TPA in atomic
systems has been made, and coverage is restricted to molecules of general interest.
There have been a number of studies of the TPA of NO, including a high-resolution
Doppler-free two-photon excitation of the A 2ci+ state. 2 4 2 In this study the
measurement of the frequency difference between TPA and the simultaneously
recorded one-photon excitation spectrum made it possible to make a direct optical
determination of the A-type doubling in the X 2 nground state. A more recent study
has investigated the high resolution of the A ,ci+ (v = 0,1,2, or 3), C2n(v = 0 or l),
and D2C+ (v = 0) states of NO.243The absorption was monitored by use of
fluorescence emission from the level reached either directly or by cascade
mechanisms from higher states. Self-quenching rate constants for the vibronic
states were obtained from a simple Stern-Volmer-type formula. The latter
application of TPA results from the advantage it has over single-photon excitation
in that it is free from the inner-filter effect. A similar study has measured ;he
quenching of the A 2 E f (v" = 0) state by collisions with ground-state NO
molecules. 244 Two-photon excitation has also been used in high-resolution studies
of the A ,C+ 245 and C 2 n246electronicstates. A study of the v 2 band of 5NH3that
uses the recently developed technique of infrared-microwave two-photon spectro-
scopy has been published.247In this technique a tunable microwave frequency is
added to or subtracted from a fixed laser frequency to give an effectively tunable
infrared source. Tuning ranges up to 10 GHz have been achieved in systems
based on the C O , laser, chosen because of its linewidth and stability. The
16 601.88cm- two-photon transition in Na, vapour is of particular interest
because of the presence of a near-resonant intermediate level which makes the
dominant contribution to the transition strength. The levels are shown in Figure 12.
The off-resonance A ( = %vat- vbJ is only 936 MHz. A theoretical and experi-
mental study of the polarization dependence for this two-photon transition has
utv
:?z
Xu ~ ' = 2 2j'=L9
. ( A1 * I
l +
~ " = 2 , j " = 5 (0X I,)
'. The OH-
*
Figure 12 Level scheme of the Na, two-photon transition at vJc = 16 601.88 cm-
resonance A = 936 ( 25) MHz
(Reproduced with permission from Chem. Phys. Lett., 1977, 50, 41)
24'
M . M. Salour, Ann. Phys. ( N . Y . ) , 1978, 111, 364.
14'
R. Wallenstein and H. Zacharias, Opt. Commun.. 1978, 25, 363.
243
M . Asscher and Y. Hass, Chem. Phys. Lett., 1978, 59, 231.
244 G. F. Nutt, S. C. Haydon, and A. I . McIntosh, Chem. Phys. Lett., 1979, 62,402.
245 Y. Takubo, S. Hasegawa, and M. Shimazu, Jpn. J . Appl. Phys., 1977, 16, 1697.
246
P. A. Freedman, Can J . Phys., 1977, 55, 1387.
247
H. Jones, J . Mol. Spectrosc., 1978, 70, 279.
shown that in the classical limit (J -+ a,a good approximation for J > 10) the
polarization behaviour is independent of the electronic symmetries and can be
different for the cases A % AvD and A x AvD (where A v D is the Doppler width)
owing to velocity tuning. 248 The effect of the near-resonant intermediate level in
Na, on the relative strengths of the Doppler-free and Doppler-broadened two-
photon absorptions has also been investigated.249
An interesting observation of two-photon excited fluorescence from the satu-
rated hydrocarbons cyclohexane, decalin, and n-pentadecane has been made. 250 A
pulsed N, laser was used for excitation, and the fluorescence spectra and lifetimes
found in the study were in good agreement with results from previous one-photon
studies. The authors estimated that 0.1 % of the laser energy was absorbed in 1 cm of
the solvents, and this should clearly be of concern to workers in this area. A recent
paper has suggested that an intense broad feature observed in the two-photon
thermal-lens spectrum of liquid benzene around 200nm does not arise as was
recently suggested from the E , valence state but is a direct two-photon excitation
into the conduction band of the l i q ~ i d . ~A" high-resolution study of the TPA
spectrum of benzene crystals in the 530400 nm region has been published. 2 5 2 The
spectra can be related to benzene molecules of approximately Cul symmetry. The
work has provided values for the two-photon tensors associated with each of the
vibronic transitions. The 1 cm- resolution two-photon excitation spectra of [ 'Ha]-
and [2H8]-toluenevapours in the region of the ' B , t ' A , transition have been
measured. 2 5 3 Ain~previous studies of benzene and its derivatives a large fraction of
the intensity occurs in a subsystem induced by an out-of-phase C-C stretch vI4(b2).
The two-photon excitation spectra of the lowest 'Bzustate of ['Hgl- and ['HJ-
naphthalene at 4.2 K have been analysed, and they show that a b,, vibration is the
most prominent perturbing vibration in the excited state and that it is also
important in the vibronic coupling between the ground and lowest ( 'Bh) excited
state. 2 5 4 The fluorescence spectrum of naphthalene vapour under collision-free
conditions has been measured following excitation into the strongest band of its
two-photon excitation spectrum. 255 The spectrum exhibits vibrational structure
superimposed on a strong non-resolved background, and it is suggested that the
background arises from further excitation of the two-photon excited state by
the strong radiation field. In contrast to naphthalene where the transition to the
lowest electronic state ' B , (Lb)is one-photon allowed but two-photon forbidden,
the transition in phenanthrene to the lowest 'A electronic state is both one- and
two-photon allowed. The one- and two-photon spectra of phenanthrene crystal at
4.2 K have been compared and show the expected one-to-one correspondence for
all the main vibronic bands.256There are, however, differences in the relative
intensities of the vibronic bands in the two spectra.
248 J. P. Woerdman, Chem. Phys. Lett., 1977, 50, 41.

249 J. P. Woerdman, Phys. Lett. A , 1978, 69, 18.
250 S. Dellonte, E. Gardini, F. Barigelletti, and G . Orlandi, Chem. Phys. Lett., 1977, 49, 596.
251 V. Vaida, M. B. Robin, and N. A. Kuebler, Chem. Phys. Lett., 1978, 58, 557.
*'* R . M. Hochstrasser, C. M. Klimcak, and G. R. Meredith, J . Chem. Phys., 1979, 70, 870.
253 R. Vasudev and J. C. D. Brand, Chem. Phys., 1979, 37, 21 1 .
254 N. Mikami and M. Ito, Chem. Phys., 1977, 23, 141.
"' H. Gattermann and M . Stockburger, Chem. Phys., 1977, 24, 327.
256 H. Otokozawa, S. Inomata, N. Mikami, and M. Ito, Bull. Chem. SOC.Jpn., 1977, 50, 2899.
42 Photochemistry
A two-photon excitation study of trans-stilbene in methylcyclohexane has
revealed a strongly allowed two-photon transition with a maximum of 41 000cm-
between the one-photon A and B bands2" This has led the authors to speculate
that this band arises from the 'phantom' singlet state which has been postulated to
be the major pathway for cis-trans photoisomerization of stilbene. A number of
calculations had previously indicated the presence of states of 'A, symmetry at
energies between those of the A and B bands (B, symmetry), and the present study
presents strong evidence based on the measurement of the polarization ratio SZ that
the overall symmetry of the newly observed state is indeed A,. The measured
spectrum and its polarization ratio are shown in Figure 13. The new state has
previously been given a ' p symbol and is regarded as two joined benzyl radicals,
each of which is separately excited, with an equilibrium geometry twisted by 90"
about the ethylenic bond from that of planar stilbene. A related study of all-trans
P
P
I .3
I .I
0.9
0.7
0.5
0.3
0.50, . ..
34400 36000 3cm 30000 42000 44000
T o t a l Encrgy/crn-l
Figure 13 (a) Upperplots. The dots are data points for the TIPE spectrum of stilbene (linearly
polarized excitation). F = sample fluorescence intensity; I = laser intensity. The ordinate
values have been multiplied by a constant before plotting (left scale). Vertical lines through the
dots indicate a change of dye in the dye laser. The solid line is the one-photon absorption
spectrum of stilbene ( 5 x solution, 1 mmpath) in units of optical density (right scale).
Positions of the A and B bands of the one-photon absorptionspectrum are indicated. (b)Lower
plot. Two-photonpolarization ratio spectrum of stilbene. R is thejuorescence intensity excited
by circularlypolarized light divided by thefluorescence intensity excited by linearlypolarized
light
(Reproduced with permission from J . Chem. Phys., 1977, 66,4540)
257
T. M. Stachelek, T. A. Pazoha, W. M. McClain, and R. P. Drucker, J . Chem. Phys., 1917,66,4540.
diphenylhexatriene (DPH) in an ether-isopentane-ethanol (EPA) glass matrix at
77K has located the origin of the 'A,-'A, two-photon allowed transition at
25 050cm- ', some 990cm- ' below the origin of the lowest one-photon allowed
'B,- 'A, transition. 2 5 8 A study of all-trans 1,3,5,7-octatetraene in n-octane at 4.2 K
has clearly established that the lowest-energy excited singlet state has even parity,
confirming its 'A, assignment, 2 5 9 and measurements of the two-photon excitation
spectrum of all-tram diphenyloctatetraene in EPA glass at 77 K have identified the
origin of the lowest-energy 'A, t 'A, transition at 22 360cm- approximately ',
'
2000cm- below the origin of the one-photon allowed 'B, t ' A , transition.260
The phosphorescence-detected two-photon excitation spectrum of triphenylene in
n-heptane single crystals at 1.6 K has been used to assign 'A'' and ' A ' , symmetry,
respectively, to the S,and S , states, in contradiction with earlier work. 2 6 1 The two-
photon absorption cross-section of the dye 7-hydroxycoumarine (umbelliferone) in
an ethanol solution has been estimated to be (7.9 f 3.9) x 10-50cm4s per
photon molecule at 60814 nm. 2 6 2
An interesting study of two-photon absorption in u.v.-transmitting materials has
been published .263 Absolute TPA coefficients were measured for a number of alkali
halides and a number of widely used harmonic-generating materials at 355 and
266nm. Amongst other things it was noted that for the alkali halides the TPA
coefficients at 355 nm were larger than those at 266 nm.
Multiphoton Absorption Processes.-A number of papers relevant to this heading
are discussed in the section on laser-induced processes. A volume of invited lectures
on multiphoton processes has been published which effectively serves as a review of
the subject. 264 The topics covered include quantum electrodynamics, resonance
fluorescence, atomic and molecular multiphoton processes, coherence and reson-
ance effects, and the relatively new subject of collisions in the presence of intense
fields. A quantum-mechanical formalism for the treatment of temporal atomic and
molecular coherence in multiphoton absorption has been published. 2 6 5
Multiphoton transitions can be conveniently divided into two categories dependent
on whether or not there are 'near resonances' in intermediate states, and the present
paper treats the case where there is no intermediate resonance. The theory provides
a basis for understanding certain features of the effects of high-intensity laser
radiation that are not compatible with kinetic equations and that arise because of a
partial coherence between the laser electric field and the electric dipoles of the
relevant absorber. In such cases it is not possible to average simply over the phases
to compute a transition rate. The treatment in the paper leads to the derivation of
multiphoton Bloch equations. Examples of the coherence effects that have been
observed are line-splitting in resonance fluorescence and ionization, isotopic
selectivity in photodissociation, and the oversaturation effect. The treatment of
258 H. L.-B. Fang, R. J. Thrash, and G. E. Leroi, Chem. Phys. Lett., 1978, 57, 59.
259
M. F. Granville, G . R. Holtom, B. E. Kohler, R. L. Christensen, and K. L. D'Amico, J . Chem. Phys.,
1977, 70, 593.
260 H . L.-B. Fang, R. J. Thrush, and G. E. Leroi, J . Chem. Phys., 1977, 67, 3389.
261
A. M. Merle, A. Campion, and M. A. El-Sayed, Chem. Phys. Lett., 1978, 57, 496.
262
L. Parma and N . Omenetto, Chem. Phys. Lett., 1978, 54, 541.
263 P. Liu, W. L. Smith, H. Lotem, J. H. Bechtel, and N . Bloembergen, Phys. Rev. B, 1978, 17, 4620.
264 'Multiphoton Processes', ed. J. H. Eberley and P. Lambropoulos, Wiley, New York, 1978.
"' P. W. Milonni and J. H. Eberly, J . Chem. Phys., 1978, 68, 1602.
44 Photochemistry
thermal perturbations in multiphoton interactions has been discussed. 2 6 6 The
analogous problems in single-photon spectroscopy are well known, namely
pressure-broadening in gas-phase studies and phonon effects in solid-state studies,
and it is usual to make one of two approximations depending on the relative time-
scales of the optical and thermal processes. If the optical process is much the shorter
of the two the statistical limit is assumed, and if it is much longer than the thermal
process the impact approximation is made. The paper establishes criteria for the
proper application of the impact limit to the calculation of multiphoton transition
rates. Reduced equations of motion have been derived for strongly driven simple
quantum systems which are modulated stochastically by coupling to a bath. 2 6 7 The
equations were applied to two examples: a randomly modulated and driven
harmonic oscillator and a modulated and damped two-level system. The effective
photon concept has been shown to predict qualitatively a number of features of
multiphoton absorption, including isotope selectivity.2 6 8 The distribution of
excited states and the average excitation level of anharmonic molecules in CW laser
beams has been considered. 269 Previous treatments have generally considered the
case of pulsed-laser excitation and V-V, V-R, and V-T energy-transfer processes,
but this present study considers either relaxation effects including diffusion and
convection. The solutions to Schrodinger’s equation for model N-level atoms and
molecules in monochromatic radiation fields have been studied numerically. 270 A
number of regularities and near-regularities were found in the population
dynamics. The following paper considers multiphoton absorption problems which
have exact solutions for the iime-dependent populations, and these are related to
observations in the numerical studies.
Linear Dichroism.-An interesting and timely collection of papers on linear
dichroism spectroscopy, most of which have appeared elsewhere in the literature,
has been published. 2 7 1 There is a continuing growth of interest in the application of
the principles of linear dichroism to studies of molecular dynamics, where the
complementary method of fluorescence emission polarization is already well
established, and in electronic spectroscopy where its use has a long but rather
limited history. In particular in recent years linear dichroism studies, often in
combination with magnetic circular dichroism studies, have made significant
contributions to the understanding of the electronic spectroscopy of a number of
important molecules, particularly aromatic hydrocarbons (vide infra). In part the
growth in interest can be attributed to the availability of new instrumental
techniques, especially those based on the photoelastic modulator, and to a sound
basis for the interpretation of the results, especially for the widely used stretched-
film method, but in general it probably simply reflects a growing recognition of the
266 A Nitzan, S. Mukamel, and A . Ben-Reuven, Chem. Phys., 1977, 24, 37.
267 S. Mukamel, I . Oppenheim, and J. Ross, Phys. Rev. A , 1978, 17, 1988.
N . S. Nogar, Spectrosc. Lett., 1978, 11, 243.
269 B. Steverding, H . P. Dudel, and F. P. Gibson, J . Appl. Phys., 1978, 49, 1260.
270 ( u ) J . H. Eberly, B. W. Shore, Z . Bialynicka-Birula, and I . Bialynicki-Birula, Phys. Rev. A , 1977, 16,
2038; (6) Z. Bialynicka-Birula, I. Bialynicki-Birula, J. H . Eberly, and B. W. Shore, Phys. Rev. A , 1977,
16, 2048.
27’
‘Proceedings of the Nobel Workshop in Lund, October 25-27, 1976, on Molecular Optical Dichroism
and Chemical Applications of Polarized Spectroscopy’, ed. B. Norden, Lund University Press, Lund,
1977. (See also Spectrosc. Lett., 1977, 10)
value of such studies. The papers in the Workshop Proceedings 271concernboth the
experimental and theoretical aspects of the subject. The applications of linear
dichroism spectroscopy have also been reviewed elsewhere 272 as has the use of
linear and circular dichroism studies in the vacuum ultraviolet region.273The
application of the piezo-optical birefringence modulator to the measurement of
Stokes parameters has been described, and it has been,illustrated by a number of
experiments. 274
An important paper has provided a theoretical basis for some basic well defined
photoselection studies for cases where high-intensity laser excitation is used. 75 For
optically thin samples general expressions are derived for the dichroic ratios of the
probe-beam absorbance for molecules having different transition-moment sym-
metries, i.e. linear, planar, or isotropic, for the cases both of steady state and of
pulsed excitation. For the limit of low excitation levels the familiar limiting values
of the dichroic ratio are recovered; e.g. for the case of the steady-state or 'long-
pulse' bleaching of parallel linear absorbers the dichroic ratio D is given by equation
(8), which for the case of low excitation intensities, a 4 1 (ais a dimensionless
2[a(3a)* - + arctan(3a)bI
(3a*
D =
2a(3a)* + (3a)* + (3a + l)arctan(3a)*
parameter equal to Imopz, where Imisthe mean excitation intensity, opthe molecular
cross-section at the excitation wavelength, and z the electronic relaxation time),
reduces to equation (9), which has the familiar limit of 3. For perpendicular
D =
("7"
+
3 I-- ... , (9)
absorbers the low excitation limit yields the expected value of !4. The variation of D
with a for 'long-pulse' excitation of linear and other symmetries is shown in Figure
14. Perhaps the most interesting result in this paper is a derivation that shows it is
possible to distinguish between transition-moment symmetries in molecules and the
different saturation behaviour of their absorbances when working with optically
thick samples. Ground-state depletion experiments using picosecond laser exci-
tation are described which distinguish the linear absorber, cryptocyanine, from the
planar absorber, gallium phthalocyanine chloride. The time dependence of
photoselection in systems where there is no rotational motion of the excited
chromophores during their lifetimes has been discussed. 276 The changes in the
photoselection due to energy-transfer processes in the limit of weak interactions is
considered, and it is suggested that it may be advantageous to measure time-
dependent photoselection rather than the anisotropy in certain situations. Studies
of laser-induced birefringence in dye solutions 277 and of a new laser method to
measure such effects 278 have been reported. A valuable paper has provided a
272
B. Norden, Appl. Spectrosc. Rev., 1978, 14, 157.
273 A. F. Drake and S. F. Mason, J . Phys. (Paris), Colloq., 1978, 212.
2'4 A. J. Wojtowicz and H. J. Lozykowski, Acta Phys. Poi. A , 1978, 54, 867.
275
B. Magde, J . Chem. Phys., 1978, 68, 3717.
276
F. Tanaka and N . Mataga, Photochem. Photobiol., 1979, 29, 1091.
277
A. M. Borch-Bruevits, T. K. Razumova, and I. 0. Starobogatov, Opt. Spektrosc., 1978, 44, 957.
278 J. J. Song, J. H. Lee, and M. D. Levenson in 'Laser Spectroscopy 111' (Springer Ser. Opt. Sci), Vol. 7,
1977, p. 450.
46 Photochemistry
completely general treatment of the time-dependent relaxation behaviour of a
monodisperse system of arbitrarily shaped rigid bodies, after initial alignment by an
externally applied field e.g. in a Kerr cell. 279 It is shown that the decay of the linear
>I
9.
0.4 - -- ...
.. .
L
0
.-cnc
\
0.2
I 1 1 I I I I
-2 -1 0 1 2 3
l o g a(
Figure 14 The anisotropy A seen by a probe beam S, related to the induced dichroism D by
+
A = ( D - 1)/(D l ) , as a function of excitation level afor long-pulse or continuous-wave
illumination. Four absorber symmetries are distinguished: --- parallel S and P linear
absorbers, -.-- perpendicular linear absorbers, * * coplanar plane absorbers, either
~
absorber isotropic
(Reproduced with permission from J . Chem. Phys., 1978,68, 3717)
dichroism, and other optical properties, in a force-free rotational diffusion process

can be described by five exponential terms.
A number of interesting spectroscopic investigations using linear-dichroism
techniques have been reported. The optical activity of derivatives of 9,9'-
spirobifluorene is of some interest, and to help interpret certain features of the
circular-dichroism spectra in these molecules it is necessary to know certain basic
information about the electronic transitions in these molecules such as their
polarization directions. The basic chromophore in these systems is biphenyl. A
linear-dichroism study of biphenyl, fluorene, 9,9'-3pirobifluorene, and 6,6-ves-
pirene in stretched polyethylene films has led to a correlation scheme which relates
the bands in the spectra of these molecules and suggests that the optical activity
arises from a dipoledipole interaction. 2 8 0 A linear-dichroism study of biphenyl,
fluorene, 4,5,9,1O-tetrahydropyrene,and 9,lO-dihydrophenanthrenein stretched
poly(viny1 alcohol) film has also been reported.28' The results were in good
agreement with calculations using an LCAO MO SCF CI method. A number of
surprising results have been obtained in a significant paper on the influence of
substitution patterns on the benzenoid 'Lb, 'La, and ' B transitions. 2 8 2 Steroid
derivatives of benzene were used to make it possible to align unsymmetrically
substituted benzene derivatives in a known way relative to the film-stretch
directions and thus to determine their polarization directions. The 'Lb intensity was
219 W. A. Wegener, R. M. Dowben, and V. J. Koester, J . Chem. Pkys.. 1979, 70, 622.
280 J . Sagiv, A. Yogev, and Y. Mazur, J . Am. Chem. SOC.,1977, 99, 6861.
T. Yoshinaga, H. Hiratsuka, and Y. Tanizaki, Bull. Chem. SOC.Jpn., 1978, 51, 996.
282 J. Sagiv, Tetrahedron, 1977, 33, 2303.
resolved into induced and vibrational components, and contrary to previous
assumptions the vibrational intensity was found to depend on the substituent and
not to be constant. The results were used to suggest a simple model which could
predict the absolute configurations of chiral benzenoid derivatives. 283 A linear-
dichroism study of perylene has been published, 284 and the long-wavelength
absorption band of indole has been investigated in a linear-dichroism study using
stretched polyethylene films. 2 8 5
A number of interesting examples of applied linear-dichroism spectroscopy
relate to studies of macromolecules or supramolecular systems. A nice example has
been the determination of the orientation of the 568 nm transition dipole moment
of the retinal chromophore of bacteriorhodopsin relative to the membrane. 2 8 6
Transient linear-dichroism measurements yielded a value of 78”, and a linear-
dichroism study in tilted membranes, a method recently treated theoretically, 2 8 7
yielded a value of 7 1”. Studies of the orientation of aromatic amino-acid residues in
rhodopsin in magnetically oriented bovine-rod outer segments 288 and the orien-
tation of the reaction centre transition moments in the chromatophore membrane
of Rhodopseudomonas sphaeroides 2 8 9 , 290 using linear dichroism and photoselec-
tion methods have been published.
Circular Dichroism.-A new theory has been proposed to describe the circular
dichroism (CD) of an achiral chromophore interacting with a number of
chromophores, which may or may not themselves be achiral, with fixed relative
orientations and negligible electron exchange. 2 9 1 Current theories of induced C D
in achiral molecules concentrate on two terms arising from a first-order perturb-
ation treatment, the static coupling term, and the dynamic coupling term.
Correction terms can arise by going to higher-order perturbation and/or through a
multipole expansion. The interesting point made by the author is that, in cases
where the dipoledipole interaction term, I/d& vanishes and the next term in the
expansion, the dipole-quadrupole interaction, Vds, is the first non-vanishing
contribution to the C D strength, it is possible to argue that just as important
correction terms could arise from second-order perturbation theory which would
lead to terms quadratic in I/d& The author develops this idea into the associate-
induced circular dichroism (AICD) theory and after deriving the second-order
terms and their symmetry properties successfully applies the theory to the case of
cyclic peptides. The possibility of using absorption-moment sum rules in the
analysis of natural and magnetic optical activity has been discussed. 2 9 2 The
minimum number of atoms required for a disymmetric molecule is four, and the
paper shows that the moment summation expressions contain terms which facilitate
the analysis of optical activity by means of four-atom clusters. A simplified version
2H3 J. Sagiv, Tetrahedron, 1977, 33, 2315.

284 Y. Tanizaki, T. Yoshinaga, and H. Hiratsuka, Spectrochim. Acta A , 1978, 34,205.
285 V. N. Umetskaya and K. K. Turoverov, Opr. Spectrosc., 1978, 44, 637.
M. P. Heyn, R. J. Cherry, and U. Mueller, J. Mol. Biol., 1977, 117, 607.
*” B. Norden, G. Lindblom, and I. Jonas, J. Phys. Chem., 1977, 81, 2086.
”’ J. F. Becker, F. Trentacosti, and N. E. Geacintov, Photochem. Phorobiol., 1978, 27, 51.
”’ C. N. Rafferty and R. K. Clayton, Biochim. Biophys. Acta, 1979, 546, 189.
*‘O A. Vermeglio, J. Breton, G. Paillotin, and R. Cogdell, Biochim. Biophys. Acta, 1978, 501, 514
29‘
P. E. Schipper, Chem. Phys., 1977, 23, 159.
*” D. Caldwell, M o f . Ph-w., 1977, 33, 495.
48 Photochemistry
of DeVoe's classical theory of molecular optical properties, which has been used
previously to calculate the CD spectra of a number of important systems, has been
developed; in it the coupled dipole oscillators of the theory are assigned Lorentzian
shapes.293In certain cases a normal mode analysis can lead to the frequency
dependence of the optical properties of the system. The present method gave a
forty-fold saving in computer time over the original method in model calculations
on a 12-residue right-handed a-helix. A scattering formalism treatment of optical
activity in absorption bands has been published,294and the application of MO
theory to sum rules 29s and to absolute conformations 296 has been discussed.
A useful review of fluorescence-detected circular dichroism (FDCD) has been
published; it describes both the equipment and calibration procedures and the
theory behind the effect, with particular emphasis in the latter of the effects of
photoselection. 297 The first reported quantitative measurements of photoselected
fluorescence-detected CD have appeared. 298 A recent theory of FDCD 299
predicted that for the case of negligible fluorophore rotation the measured FDCD
signal OFo is given by the simple expression given in equation (lo), when the angle
that the detected polarization makes with the axis perpendicular to the excitation
beam is 35.25" and where R and D are the average rotational and dipole strengths,
respectively, AA is the difference between left and right circularly polarized
absorbance, and A is the absorbance. The values in the brackets in the expression
can be obtained from separate measurehents of the CD and absorption spectra of
the sample, and therefore as a test of the theory 8," was measured as a function of
both wavelength and the polarizer angle, with good agreement expected when the
latter was 35.25'. The results for solutions of lo-[2H]camphorsulphonic acid in
glycerol are shown in Figure 15, and the agreement between theory and experiment
is seen to be good. An important potential application of the method is in the study
of local conformations in macromolecules, and the paper reports that preliminary
measurements have resulted in a value for 4R/D of the single tryptophan residue in
human-serum albumin accurate to +30%, which is clearly enough at least to
determine its sign. There is, however, apparently a serious artifact problem when
using the technique. An FDCD study of the uranyl ions in Na[UO,(MeCOO),] has
also been published. 300
The application of phase-modulation spectroscopy to the measurement of
circular dichroism in the presence of strong linear dichroism, as is found in
anisotropic single crystals such as the A( + ),-tris(ethylenediamine)cobalt(III)
complex, has been discussed. CD and ORD studies of biological systems in an
293 J. Applequist, K . R . Sundberg, M . L. Olson, and L. C. Weiss, J . Chem. Phys., 1979, 70, 1240.
294 A. Traspaderne and F. Castano, Chem. Phys. Lett., 1978, 56, 318.
295 D. Caldwell, Proc. SOC.Photo.-Opt. Instrum. Eng., 1977, 112, 138.
29b G . Snatzke, Angew. Chem., 1979,91, 380.
29'
D. H. Turner, Methods Enzymol., 1978, 49, 199.
298
E. W. Lobenstine, and D. H . Turner, J . Am. Chem. SOC.,1979, 101, 2205.
299 I. Tinoco, jun.,B. Ehrenberg, and I. Z. Steinberg, J . Chem. Phys., 1977, 66, 916.
300 K. Murata, Y. Yamazaki, and M. Morita, J . Lumin., 1979, 18/19,407.
30r H. P. Jensen, Chem. Phys. Lett., 1977, 52, 559.
electric field have been reviewed,302 and a microscopic and macroscopic description
of changes in the polarization state of light on passing through gases and liquids has
been developed which is based on the behaviour of the Stokes parameters. 3 0 3 There
I
i I I 1 I i I
t
z
,
I
0-
ou-
Q)
-
-0.2 -
-
-0.4 -
-
-0.6 -
-0.0 -
I I 1 I I I I I 1
x /nm
Figure 15 Photoselected FDCD spectra of 0.43 M 10-d-camphorsulphonic acid in glycerol:
(-) Q, = O", (---) Q, = 35", (--.--.) Q, = 90", (x) spectrum predicted from c.d. and
adsorption spectra. Base-line solution was 1.O x M DL-tryptophan in water. Filter was
Corning 4-72 and cell path length was 1 m m
(Reproduced with permission from J . Am. Chem. SOC.,1979, 101, 2205)
have been interesting reports of the asymmetric synthesis of N-methyl-

dihydroindoles 304 and of the asymmetric destruction of 1- p y r a z o l i n e ~ ,both
~~~
using circularly polarized light. Vacuum U.V. CD measurements have been
reported for protected homoligomers derived from L-leucine 306 and for polyvaline
and polyproline, 307 and an instrument suitable for making such measurements has
been described.308
A study of the induced CD spectra of homo- and hetero-disubstituted benzene
derivatives in cholesteric liquid-crystal solution supports a vector-addition model
for the resultant transition moment in which the 'L, and 'Labands in the parent
302 I . Tinoco, jun., Electro-Opt. Ser., 1976, 1, 367.

303 L. Knoell and R. Rost, Exp. Tech. Phys., 1977, 25, 261.
'04 J. F. Nicoud and H. B. Kagan, Isr. J . Chem., 1977, 15, 78.
305 M . Schneider, 0. Schuster, and H. Rau, Chem. Ber., 1977, 110, 2180.
306 M. M. Kelly, E. S. Pysh, G. M. Bonora, and C. Toniolo, J. Am. Chem. Soc., 1977, 99, 3264.
307 E. S. Pysh, Jerusalem Symp. Quantum Chem. Biochem., 1977, 10, 409.
308 A. Gedanken and M. Levy, Rev. Sci. Instrum., 1977, 48, 661.
50 Photochemistry
hydrocarbon are assigned, respectively, to the ' A , , -, 'B2, and the ' A , , -, ' B , ,
transitions. 309 A U.V.and C D study of chiral pyrazines has led to the assignment of
symmetry labels to the excited states in these molecules. 310 The origin of the C D of
the 300 nm carbonyl n* + n transition in ( + )-D-camphor has been investigated by
means of time-dependent Hartree-theory calculations in the random-phase
coupled-oscillator approximation. ' The C D is shown to arise from the coupling
of the magnetic-dipole transition moment with the backbone density of states; the
coupling of the electric-dipole moment is negligible by comparison. The coupling
itself was found to be dominated by the associated electric-quadrupole transition
moment. The contribution of aromatic side chains to the far-u.v. CD of peptides
and proteins has been calculated by considering the rotational strength of the L,
transition in phenylalanine and tyrosine side chains of dipeptides and tripeptides in
various conformations, and a frozen-core MO procedure was used to calculate
the long-wavelength chiroptic properties of oligopeptides in the parallel-chain
pleated sheet and poly(L-proline) I and poly(L-proline) I1 conformations. '
A major series of papers has been published on the magnetic circular dichroism
(MCD) of cyclic n-electron systems. l4 An essentially descriptive non-quantitative
theory of the absolute MCD signs for electronic systems derived from a (4N + 2)-
electron perimeter is developed and successfully applied to a number of groups
of molecules. The MCD of a molecular electronic transition at 4 particular
wavelength is expressed by the magnetically-induced molar ellipticity [el,
per unit magnetic field, which, for an isotropic sample, is given by
[a, = -21.3458[f,(B + C/kT) + flA], where fi is the absorption lineshape
function andf, its derivative, and A , B, and C are the Faraday parameters of the
transition. The MCD spectrum will be a sum of the contribution from each
transition at any given wavelength. In MCD studies attention is focused in
particular on the B parameter as C vanishes in molecules with a non-degenerate
ground state (as is often the case, including the molecules considered in the present
study) and A vanishes if the excited state is non-degenerate. The theory of the
present work is developed by using the classical n-electron perimeter model of Platt
to derive explicit algebraic expression for A and B after first deriving the singlet
wave functions for the two B and two L states. The effect of various perturbations
on A and B such as ring-carbon replacement or substitution is analysed by looking
at the effect of the perturbation on the configuration mixing for the unperturbed
perimeter case. Thus the changes in the MCD signs brought about by a
perturbation arise from the latter's effect on the MO energies. These energychanges
are discussed in terms of AHOMO (highest occupied MO) and ALUMO (lowest
unoccupied MO), where the former symbol represents the absolute value of the
energy difference of the two orbitals of the perturbed annulene which originate in
the HOMO orbitals of the parent ( $N, $-,,,) and the latter for that of the two orbitals
which originate in the LUMO orbitals of the parent ( $N+ ,, $- N - ,). On the basis of
the relative sizes of AHOMO and ALUMO, chromophores are divided into 'soft'
309 W. G. Hill, S. F. Mason, and R . D. Peacock, J . Chem. Sor., Perkin Trans. 2, 1977, 1262.
310 G. Snatzke and G. Hajos, Jerusalem Symp. Quantum Chem. Biochem., 1977, 10, 295.
311 J . Texter and E. S. Stevens, J. Chem. Phys., 1978, 69, 1680.
312 R. W. Wood, Biopolymers, 1978, 17, 1451.
3'3 M . Iseli, R . Geiger, and G . Wagniere, Helv. Chim. Actu, 1978, 61, 171.
3'4 J . Michl, J. Am. Chem. Soc., 1978, 100, 6801, and following papers.
and 'hard' categories, the former for cases where AHOMO z ALUMO and the
latter for cases where M O M 0 # ALUMO. As may be guessed, the MCD signs
for soft chromophores are sensitive to perturbations whereas those for hard
chromophores are less so. Following discussions of the algebraic solution of the
perimeter model for the A and B terms of high-symmetry systems with a (4N + 2)-
electron [n]annulene perimeter l4 and for the B terms of lower-symmetry systems
with the same perimeter,31 a general classification of all chromophores with this
perimeter is developed. 3 1 The latter paper gives useful general rules for the effect of
mesomeric and inductive substituent effects on various kinds of soft MCD
chromophores, and the results for systems with an uncharged perimeter are given in
Table 4.The predictions are then illustrated by experimental investigations of the
MCD of a range of cyclic n-systems, the results of which are presented in the 15
papers following reference 3 16. The systems discussed are as follows: aza analogues
of benzene, pyridine derivatives, pyridones and related heterocycles, aza analogues
of naphthalene, naphthalene derivatives, aminoquinolines and aminoisoquinol-
ines, quinolones, isoquinolones, and related heterocycles, aza analogues and
derivatives of anthracene, aza analogues of phenanthrene, pyrene derivatives,
azulene derivatives, benzazulenes, acenaphthylene, fluoranthene, and finally
benzofluoranthenes. The papers represent a major contribution to the wider
recognition of MCD spectroscopy as a generally useful method.
An additional feature of the above papers is that they give a valuable insight into
the success, or otherwise, of various approximate methods of calculation of the
MCD properties of molecules. In particular the previously successful application of
simple PPP calculations, especially to non-alternant hydrocarbons, is somewhat
fortuitous and cannot be expected to apply in other systems, e.g. linear n-systems.
The shortcomings of the simple PPP model are most exposed when dealing with soft
chromophores, and its improvement by the inclusion of overlap between the basis
2p orbitals in z-electron calculations has been investigated in a study of systems
with approximate alternant pairing symmetry. l 7 The failure of the simple PPP
model to calculate the B terms of alternant hydrocarbons has prompted a study of
phenanthrene, using an extended PPP method. The calculated B-term signs were
mostly correct, but there were large differences between the calculated and
experimental B-term magnitudes. * The magnetic rotational strengths and dipole
strengths of the symmetry-forbidden transitions, 'Al, + 1B2uand 'Alg + ' B I u ,
in benzene have been calculated. 319A theory of the MCD saturation effect in which
systems with a paramagnetic ground state deviate from a simple magnetic-
field-temperature-dependence behaviour at high field and/or low temperature has
been published. 3 2 0 The results are generalized to include magnetic circularly
polarized luminescence (MCPL) and the effects of photoselection. A cryostat
'I5
J. Michl, J . Am. Chem. Sor., 1978, 100, 6812.
3'h J. Michl, J . Am. Chem. SOL..,1978, loQ, 6819.
317 N. H. Joergensen, P. B. Pedersen, E. W. Thulstrup, and J . Michl, Int. J . Quantum Chem..Symp.. 1978,
12, 419.
31H ( a ) E. W.Thulstrup,J. Mol. Structure. 1978,47,359; ( b )E. W. Thulstrup, f n t .J . Quantum Chem.. 1977,
12 (Supplement I ) , 333.
"' S. T. Lee, Y . H. Loon, H. Eyring, and S. H . Lin, J . Chem. Phys., 1977, 66, 4349.
320 P. N . Schatz, R . L. Mowery, and E. R. Krausz, Mol. Phys., 1978, 35, 1537.
Table 4 Sign of (AHOMO - AL,UMOy for uncharged-perimeter soft chromophores
Subst ituent efec ts
-~
Chromophore Posit ion +I -I +I? -I? Example

Double-soft 0 0 - +
Even-soft DS -0 -0 - -, then 0, then +
0-
N 0 0 -0, then - -0, then +
SD -0 -0 + , then 0, then - +
Odd-Soft D - + - t
N 0 0 -0, then - -0, then +

S + - +, then 0, then - -, then 0, then +
-3
a A positive sign implies a + , -, + , - sign sequence for substituent-inducedp + contributiond to B terms of the L and B bands in the order of increasing energy; a negative sign *
implies the -, +, -, + sign sequence. 'Changes which occur as the E effect gradually becomes stronger are noted. h
r,
P2
h
.2
suitable for MCD and MCPL studies has been described.321The application of
MCD and electrochromism studies to investigations of molecular Rydberg states
has been discussed.322
Stark and Related Effects.-An interesting area of application for studies of the
electric-field-inducedchanges in the absorption and emission spectra of molecules,
i.e. the molecular Stark effect known as electrochromism, is the monitoring of
membrane potential with dye-molecule probes. The studies are complicated by the
possibility of several different mechanisms for changes in the spectral properties of
the optical probes; for example there may be a potential-dependent partition of the
dye between either the cell interior and the external medium or the membrane and
the external medium, there is the possibility of a potential-dependent dimerization
within the membrane, and finally there is the possibility of a direct response to a
local potential which develops subsequent to energization. The above mechanisms
have been variously invoked to account for a wide range of observations with a
variety of probe-membrane systems. There are very few cases, if any at all, where
the electrochromism mechanism has been shown to be dominant. A recent paper
has discussed the desirable features of an electrochromic probe.323 Extended
Hiickel (EH) MO calculations were used to calculate the change in the charge
distribution for the HOMO-LUMO transition in the chromophore which,
following self-consistent charge calculations in which the fixed EH parameters are
re-adjusted, :i used to calculate the electrochromism from the simple equation_
hAv = - qS'.E,where q is charge, 7 the distance it migrates upon excitation, and E
the electric field. The authors have identified a promising charge-shift chromophore
-
for electrochromism studies, namely the 4-@-aminostyryl)pyridinium cation
which, for a typical membrane electric-field strength of lo5Vcm- ',has predicted
Av of 24 cm- '. For the probe (3), 4-(4-dipentylaminostyryl)-l-methylpyridinium
iodide (di-5-ASP), which has a peak absorbance at 500nm, this frequency shift
-
(3)
corresponds to a shift of 0.6 nm or an OD change at 500 nm of 1.3%, both of
which are easily detectable changes. For molecular electronic transitions in which
there is no change in dipole moment on going from the ground to the excited
electronic state electrochromic effects may arise from differences in the ground- and
excited-state polarizabilities, i.e. from induced dipole moments. The discrepancies
between observed and calculated values of these polarizability changes for a
number of aromatic hydrocarbons have been discussed.324Acritical comparison of
sixteen equations in the literature which have been proposed to express the shifts in
the absorption and emission maxima of molecules in solution on changing the
solvent, i.e. solvatochromism, has been published. 3 2 5 In these equations the
321 E. R. Krausz, R. L. Mowery, and P. N. Schatz, Ber. Bunsenges Phys. Chem., 1978, 82, 134.
322 J. D. Scott, W. S. Felps, and S . P. McGlynn, Nucl. Instrum. Methods, 1978, 152, 231.
323 L. M. Loew, G. W. Bonneville, and J. Surow, Biochemistry, 1978, 17,4065.
324 G. Barnett, Int. J. Quantum Chem., 1977, 12, 427.
325 B. Koutek, Collect. Czech. Chem. Commun.. 1978, 43,2368.
54 Photochemistry
solvents are characterized by their dielectric constant and their refractive index. The
experimental data for compounds with a wide range of excited-state dipole
moments, p, were used as a basis for the comparison, and the results were also
compared with values for peobtained from separate electro-optical experiments. A
theory proposed by Bilot, Kawski, and Bakhshiev was found to be the most
satisfactory.
The electronic properties of the 2'A state of methylene (attention is usually
focused on the 3 B , and ' A states - vide supra) have been calculated using MCSCF
and extended CI wavefunctions. 3 2 6 The dipole moments in the two ' A states were
calculated for different non-linear geometries. Calculations of the dipole moment
functions of the a3nand A ' n states 3 2 7 and the d 3 Aand states 3 2 8 of CO have
been published, the latter being in good agreement with available experimental
data. A study of the electrochromism spectrum of the 174.9nm transition in
formaldehyde supports the assignment of the excited state as the 3s(a,) +-- n(b,),
B , +- A molecular Rydberg. 329 The dipole moment in the excited state was found
to be much smaller than in the ground state. An interesting paper has used a visible-
dye laser in a laser-Stark spectroscopy study of the 2 * A 2 - X ' A' transition in
thioformaldehyde. 330 Measurements in the 401vibronic band yielded a value of
0.79 0.04 D for the excited-state dipole moment, which compares with a value of
1.56 f 0.07 D for the corresponding state in H,CO. Strong structural: features
have been observed in the electrochromic spectrum of benzene embedded in
polymer sheets,331and similar dipole-moment changes on excitation to the lowest
' n e and 3n71* excited states of p-methylbenzaldehyde and p-chlorobenzaldehyde
have been found in studies of the Stark splittings in the phosphorescence excitation
and phosphorescence spectra of these compounds in a p-dimethoxybenzene host
crystal.332 The results in the latter, study are contrary to the predictions of
qualitative arguments and may indicate a strong mixing of the 'n7ic and 37r7Pstates.
The effect of vibronic coupling between 3ncP and 3n7P states on the dipole moments
in the triplet states of aromatic aldehydes has been discussed. 3 3 3 The excited-state
dipole moments of various nitrobenzene derivatives have been obtained from MO
calculations and studies of solvatochromic effects.334 The results were used to
compare critically a number of theoretical expressions for solvatochromism (see
reference 325). Dipole moments for a number of exciplexes formed between
heterocyclic compounds and aromatic hydrocarbons and amines have been
obtained from measurements of the solvent shifts of their emission bands,335and
accurate excited-state dipole moments for several exciplexes of 9,l O-di-
cyanoanthracene and NN-dimethylaniline have been obtained from emission
electrochromism studies. 3 3 6 An interesting study of the dipole moments in the
326 C. W. Bauschlicher, jun. and D. R . Yarkony, J . Chem. Phys., 1978.69, 3875.
3'7 J . M . Norbreck, R . R. Merkel, and P. R. Certain, Mol. Phys.. 1977, 34, 589.
328
K . Kirby and B. Liu, J . Chem. Phys., 1978, 69, 200.
320 G. C. Causley and B. R . Russell, J . Chem. Phys., 1978, 68, 3797.
330 R. N. Dixon and C. R . Webster, J . Mol. Spectrosc., 1978, 70, 314.
33' A. Davidsson, Chem. Phys.. 1978, 35, 413.
332 M. Hossain and D. M. Hanson, Chem. Phys., 1978, 30, 155.
333 L. Goodman and I . Ozkan, Chem. Phys. Left.. 1979, 61, 216.
334 S. Millefiori, F. Zuccarello, and G . Buemi, J . Chem. SOC.,Perkin Trans. 2, 1978, 849.
335 R. S. Davidson, A. Lewis, and T. D. Whelan, J . Chem. SOC.,Perkin Trans. 2, 1977, 1280.
33h E. J . J . Groenen and P. N. T. Van Velzen, Mol. Phys., 1978, 35, 19.
ground and 'L, and 'Lbstates of indole and some of its derivatives uses previously
published data on solvent-dependent Stokes shifts and the results of MO SCF PPP
calculations. 3 7 Solvent-dependent Stokes-shift measurements have been used to
calculate the excited-state dipole moments of 1,3-dipheny1-2-pyrazolines in good
agreement with the results of CNDO calculations.338 Detailed studies of the
solvatochromism of merocyanine derivatives 339 and of all-trans-retinal and all-
trans-retinylidene-n-butylamine 340 have also been published.
A new method for the calculation of ground- and excited-state molecular
polarizabilities has been developed and applied to a number of molecules.341It
combines second-order perturbation theory with the CNDO/S CI method and
gives reasonably accurate polarizability tensor components for all the states
included in the CI in one calculation, in strong contrast to an alternative method
which requires at least 21 individual CI calculations for each state. The theory of the
Stark effect for atoms in a constant electric field 342 and the role of resonant Stark
broadening theory in understanding the mechanism of the collision-free dissoci-
ation of molecules in high-intensity laser resonant fields 343 have both been
discussed. The origins of the a.c. Stark effect have been reviewed in a general
discussion of level distortions in atomic systems subjected to strong laser fields. 344
Strong resonance effects are observed in these systems which on the basis of
perturbation theory arise from terms in which the factors w,,, f wp,where wpis the
laser-field frequency and w,,, the resonant frequency for the transition n + rn,
occur in the denominators of expressions for the level shifts.
A theory of electric-field-induced radiationless transitions in isolated molecules
has been published. 345 The perturbation Hamiltonian H,is given by the expression
H , = HNR + i.where ; HNR is the familiar perturbation arising from the nuclear
kinetic-energy operator, the electric field, and the transition dipole-moment
operator. The final expression for the non-radiative transition rate constant, kmg,, of
molecules with a permanent dipole moment in gaseous or liquid systems is given in
equation (1 l), where is the vibrational factor, which is unaffected by the field,
k,,, = dh2C X (cth+phwj + u)JjEjuc2

J V=+1
and J, is the electronic factor, which is affected by the field and from which the
squared field-strength term has been extracted. Rough estimates of the ratio r
between the value of kzz.with and without an electric field give values in the range
0.02 < r < 2, which should be readily detectable. Such effects may be partly
responsible for the effects of electric fields on the recombination luminescence of
electron<ation geminate pairs in sensitized low-temperature alkane glasses (see for
example reference 346).The application of a new method for the determination of
337
M. Sun and P. S. Song, Photochem. Phorohiol., 1977, 25, 3 .
338
H. Giistcn, G. Heinrich, and H. Friihbeis, Ber. Bunseng. Phys. Chem., 1977, 81, 810.
J3q A. Le Beuze, A Botrel, A . Samat, P. Appriou, and R. Guglielmetti, J . Chim. Phys., 1978, 75, 255.
340 J . P. Corsetti and B. E. Kohler, J . Chem. Phys., 1977, 67, 5237.
341 F. T. Marchese and H . H. Jaffe, Theor. Chim. Acta, 1977, 45, 241.
342 I . W . Herbst and B. Simon, Phys. Rev. Lett., 1978, 41, 67.
343 E. V. Shuryak, Kvantovaya Elektron. (Moscow), 1978, 5 , 1796.
344 J . S. Bakos, Phys. Rep., 1977, 31, 209.
345 W. Strek, Chem. Phys. Lett., 1978, 57, 121.
346 J . Bullot, P. Cordier, and M. Gauthier, J . Chem. Phys.. 1978, 69, 1374.
56 Photochemistry
dipole moments of molecules in solution by observing the effect of electric fields on
their fluorescence properties has been reported, 347 and the observation of electric-
field quenching of the fluorescence of X-metal-free phthalocyanine indicates that
the first excited singlet is directly involved in carrier photogeneration.348 A Stark
spectroscopy study and a modulated phosphorescence polarization technique have
been used to investigate the interactions between the T , and T , states of
benzaldehydes in the crystalline state. 349 The results indicate that both second-
order vibronic spin orbit and direct environmental mixings occur between the %7r*
and ’n71‘ states.
The optical analogue of the n.m.r. rotary saturation effect, in which an r.f.
standing-wave Stark electric field is tuned in rotary saturation resonance with the
splitting, has been demonstrated and analysed. 350 The production of permanent
giant dipole moments in the photolysis of spiropyran solutions in the presence of
electric fields has been demonstrated 3 5 1 and a model for photo-induced polariz-
ation or depolarization discussed. 352
A number of papers on electric-field effects in systems of biological interest have
been published, of which mention is only made of a valuable review of the role of the
’
electric field in photosynthesis 53 and of interesting observations of electrochromic
effects on bacteriorhodopsin (bR 70) in purple membranes from Halobacterium
hal~bium.~~~
4 Intramolecular Excited-state Decay Processes

Theories of Radiative Decay Processes.-The validity of the four principal rules of
organic molecular fluorescence, namely Stokes’ law, Vavilov’s law, Kasha’s rule,
and the radiative lifetime relation have been discussed by Birks.355A quantum-
mechanical theory of delayed temperature-dependent fluorescence from a poly-
atomic molecule in a dense medium or in the high-pressure gas phase has been
published. 5 6 This phenomenon, otherwise known as E-type delayed fluorescence,
is exhibited typically by organic dye molecules such as fluorescein and eosine in
glasses, and, as is well known, on the basis of a simple kinetic model it arises from a
thermally activated reversal of the intersystem-crossing (ISC) process from S1,the
lowest excited singlet state, to the manifold of T,, the lowest triplet excited state,
and thus has the temporal properties of the triplet state and the spectral properties
of the excited singlet state. The theory is developed by first considering the
molecular-level structure not in terms of zero-order pure-spin Born-Oppenheimer
basis states but true ‘molecular eigenstates’ that are constructed from the {1S>}
and { 1 T > ] vibronic manifolds and denoted by {fj> ] and characterized by their
density of states p,(E) and their decay widths y,((El). The host medium is assumed to
347 W. Baumann, J . M o l . Strucr. 1978, 47, 2 3 7 . , *
”* E. R. Menzel and Z. D. Popovic, Chem. Phys. Lett., 1978, 55, 177.
jqYM . Koyanagi, K. Higashi, and Y. Kanda, Chem. Phys. Lett., 1977, 52, 184.
3s0 Y. Prior and J . A. Kash, Phys. Rev. A , 1978, 18, 2603.

j 5 ’ V. A. Krongauz and E. S. Goldburt, Chem. Phys. Lett., 1979, 60, 251.
3 s 2 F. Fischer, Phys. Status Solidi A , 1979, 52, 189.

3 5 3 H. T. Witt, Biochim. Biuphys. Acta, 1979, 505, 355.
3 s 4 G. P. Borisevich, E. P. Lukashev, A. A. Kononenko, and A. B. Rubin, Biochem. Biuphys. Acta. 1979,
546, 171.
3 s s J. B. Birks in ‘Research in Photobiology’, ed. A. Castellani, Plenum, New York, 1977, p. 15.
3 5 6 R. Van der Werf, D. Zevenhuijzen, and J. Jortner, Chem. Phys., 1978, 27, 319.
behave just as a heat bath, i.e. to be inert, and furthermore the thermal vibrational
relaxation and excitation rates are assumed to be much greater than the relevant
intramolecular decay widths, and the widths of the resonances are assumed to be
considerably smaller than the thermal energy B- 5 kT. The total decay rate, k,,,,of
the IS> + 1T> manifold prepared by a rapid ISC process from the initially
optically excited ( I S > } manifold is given by equation (12), where 2
'f
k,, = ; dEP,bWXP(- BE)Y,(E)
[ = JdEplE)exp( - BE)] is the partition function. This expression can be developed

(12)
to obtain the quantum-mechanical equivalents to the rate constants of a simple

kinetic model for E-type delayed fluorescence, and the results are compared in
Table 5 . The new theory completely justifies the form of the phenomenological
Table 5 Correspondence between kinetic and quantum-mechanical results for EDF
Kinetic Quantum mechanic
equations derived from the kinetic model but naturally gives a great deal more
insight; in particular it provides explicit expressions for the temperature depen-
dence for the kinetic model rate parameters. This important paper concludes by
applying the theory to recent experimental data for the dicarbonyl molecule
biacetyl, which is an example of a molecule with intermediate level structure. An
equally interesting and related paper has discussed the process of inverse electronic
relaxation (IER), in which the thermal excitation process just discussed is replaced
by a multiphoton excitation of a ground electronic state { 1G > >.3 5 7 The process has
been proposed to explain the recent observation of prompt fluorescence from
CrO,Cl, following N-photon excitation ( N z 16). The theoretical problem is to
account for the apparent reversal of the decay of a 'doorway' state to a dense
manifold of a lower electronic state, a process which exhibits practical irreversibility
in the statistical limit. The difficulty is overcome by considering the scrambled
molecular eigenstates of the isolated polyatomic molecule represented by
>
( ( 1 Ga > + (1S/?> }), which are reached by incoherent multiphoton excitation.
The IER process is then regarded as the one-photon spontaneous decay of these
scrambled states due to their (lS/3>} character. The final decay channel, being a
radiative continuum, ensures the irreversibility of the IER process. The model is
illustrated in Figure 16 along with that for the process of inverse predissociation,
which except for the difference in the initial state is clearly an analogous process.
357
A. Nitzan and J. Jortner, Chem. Phys. Lett., 1978, 60, I .
58 Photochemistry
There are many examples now known of molecules in which the vibrational times
are slow enough to be comparable with radiative decay times, i.e. 10- s and above. '
For large molecules in condensed phases vibrational relaxation times are of the
Inverse Predissociation
Radiative Dissociative
con t inu u m ; : m $
Inver se Etec t ronic Relaxation
Radiative I nt ram ole c ula r

con tin u u m quasicen tinuu m
1g> 1-
-
Figure 16 Schematic representation of molecular inverse predissociation and of inverse
electronic relaxation in range ( A ) of polyatomic molecules
order of 10- l 2 s, and for such cases the large differences in the characteristic times
of the two decay processes permit a decoupled description of the overall decay. In
cases where the times are comparable this is clearly not valid. A unified theory of
relaxation and luminescence has been published which is based on the master
equation (1 3), where P, is the probability of occupation of the mth level, a,,, is the
radiative decay rate of level rn, and ymn is the relaxation decay rate of the transition n
to rn.358 The initial condition P,(O) is established by the method of excitation, and
the o! and y values can be calculated from microscopic parameters. The above
equation can then be solved for P,(t), giving the excitation distribution at any time
t , which may in turn be used to calculate quantities such as the fluorescence
quantum yield (the new theory includes radiationless decay terms), fluorescence
358 V. Seshadri and V. M . Kenkre, Phys. Rev. A , 1978, 17, 223.

intensity, and the frequency-resolved intensity. The master-equation theory in the
paper is in contrast to microscopic approaches to the problem as, for example, in
the well known theory of Nitzan and Jortner. Steady-state expressions for the
concentration of two- and three-level molecules and the corresponding lumines-
cence radiance expressions have been published. 359 This follows earlier treatments
of two- and three-level atomic systems. Experimental information on the angular
distribution of fluorescence from thick liquid layers by evanescent waves has been
shown to agree with Fresnel's theory and an effective thickness formulation, 360 and
the calculation of excited-state radiative lifetimes using a polarization propagator
approach has been described.36'
The visible and near-infrared spectrum of NO, is complex, and there are a
number of unexplained anomalies in the corresponding fluorescence spectrum. A
new model of induced coupling between the two lowest excited electronic states, 2B
and 2B2,has been proposed to explain features in the fluorescence spectrum, in
which it is assumed that a 2Bl and a 2B2vibronic level are accidentally degenerate
and that each state is coupled to a manifold of 2A ground-state vibronic levels.3 6 2
The one or more actual states of the 2A manifold that are involved are referred to
as messenger states. The model was used to reproduce a recently measured 593.5 nm
laser-excited fluorescence spectrum with considerably more success than a model
with pure ,El or 2B, initial vibronic states. Some preliminary results of an ab initio
CI calculation of the radiative and non-radiative decay of a number of vibronic
levels of the first excited singlet state, ' A 2 ,in formaldehyde have been published.363
The normal modes 4, 5, and 6 were shown to be of about equal importance for
inducing the radiative transition. The inductive effect arising from polar sub-
stituents has been shown to influence the luminescence of naphthalene 364 and
anthracene 365 derivatives by establishing that a correlation exists between
photophysical properties of these molecules and the Taft polar-substituent
constants. The enhanced diffuse reflectance at 685nm of Ocean waters rich in
chlorophyll has been accounted for by including a chlorophyll a fluorescence
contribution in the general radiative transfer equation. 3 6 6 A valuable general
article on the luminescence of aromatic- molecules with non-bonding electrons
discusses the influence of vibronic interactions on their radiative transitions in both
the weak and strong coupling limits, i.e. where the interaction energy between low-
lying nn? and nn? states is smaller or larger, respectively, than the zeroth-order
electronic-energy gaps. 3 6 7
An interesting paper has treated theoretically the phenomenon of amplified
spontaneous emission (superfluorescence - see later section also) in fluorescent dye
solutions excited by intense picosecond light pulses. 368 The rate equations derived
359 G. D. Boutilier, J . D. Winefordner, and N . Omenetto, Appf. Opt., 1978, 17, 3482.
360 E. H. Lee, R . E. Benner, J . B. Fenn, and R. K . Chang, Appl. O p t . , 1979, 18, 862.
3'1 E. Dalgaard, J . Phys. B, 1977, 10, 147.
3b2 M . Gerloff, P. Russegger, and J. Brickrnann, Ber. Bunsenges. Phi's. Chem.. 1979, 83, 108.
363 J. M . F. Van Dijk, M . J . H . Kernper, J . H . M . Kerf, H. M . Buck, and G. J. Visser, Chem. Phys. Lett..
1978, 54, 354.
L. A . King, J . Chem. SOC.,Perkin Trans. 2 , 1978, 472.
'"
'64
L. A. King, J . Chem. SOC.,Perkin Trans. 2 , 1977, 919.
"' H. R . Gordon, Appl. Opt., 1979, 18, 1161.
3'7 E. C. Lirn in 'Excited States', ed. E. C. Lim, Academic Press, New York, 1977, Vol. 3, p. 305.
''' A. Penzkofer and W. Falkenstein, Opt. Quantum Electron., 1978, 10, 399.
60 Photochemistry
from a nine-level scheme were solved numerically to investigate the effect of pump-
pulse parameters, geometrical factors, and dye characteristics on the efficiency of
amplified spontaneous emission (I,) and to establish conditions where either it is
negligible or it is large enough to generate new light pulses at frequencies different
from the pump-pulse frequency. For example, it is shown that for the results of a
fluorescence study to be free from the effects of I , then the expression (14) holds,
where N is the population, z the path length, and r~ the relevant cross-section.
For C = 10-5Mdm-3 ( N = 6 x l O ” ~ m - ~ )z, = lcm, and (gem- cex)=
2.10- l 6 cm-, the amplification is less than two. A simple model for the interaction
of two laser pulses propagating in a fluorescent dye medium has been successful
in qualitatively accounting for the results of recent experiment^.^^' In essence the
rate-equation analysis shows that the leading pulse is attenuated by absorption
and the second pulse is amplified by spontaneous emission, its amplifi-
cation depending on the delay between the two pulses. A theoretical analysis of the
design of organic compounds to optimize their lasing characteristics has been
published.370
Theories of Radiationless Decay Processes.-A major experimental and theoretical

study of the radiationless relaxation and optical dephasing of a large optically
excited isolated molecule has been published. 3 7 Narrow- and wide-band coherent
laser excitation and broadband incoherent excitation were used in a study of
pentacene in a p-terphenyl host matrix at temperatures of 1.8K and above to
explore such questions as whether or not radiationless transitions depend on the
nature of the exciting field. Optical nutation measurements (in which the ground-
state and excited-state populations oscillate at the Rabi frequency determined by
the transition dipole moment, g, and the laser-field amplitude, E), optical free-
induction decay measurements (in which a group of molecules in resonance with a
coherent field is suddently switched off-resonance and thereupon emits, initially at
least, in-phase), and incoherent resonance decay measurements (which, unlike the
previous two techniques, which are observed along the path of the laser beam, is
observed at right angles to the laser beam as incoherent spontaneous emission) were
all used to obtain the values of T , , the optical longitudinal relaxation time, and T,,
the optical transverse relaxation time, T Ibeing a measure of the decay of and T , a
measure of the dephasing of selectively prepared vibronic levels. The theoretical
model is basically a two-level scheme involving ground- and first excited-state
levels, lo> and lp>, respectively, to which a manifold of effective levels {I/>}
(which in pentacene corresponds to the triplet manifold) is added. Two limiting
time regimes are considered in the analysis, the transient coherence and the steady-
state coherence regimes, in which the observed transient decay time, T ~ ,is
comparable to or greater than the Rabi nutation time h / p ( = 27.3 ns for these
experiments), respectively. At 1.8 K the value of optical T , found for pentacene was
369 D. Faubert, S. L. Chin, M. Cormier, and M. Boloten, Can. J . Phys., 1979, 57, 160.
370 C. Rulliere and J. Joussot-Dubien, Rev. Phys. Appl., 1979, 14, 303.
37’ T. E. Orlowski and A. H. Zewail, J . Chem. Phys., 1979, 70, 1390.
44ns, which was approximately twice the value of optical T , , and this indicates that
spontaneous emission was the source of dephasing at this temperature. Optical T,
arises from radiative and non-radiative decays to the ground state and did not
change with changes in the temperature. In contrast, optical T , was found to
depend on temperature. The optical T , process has contributions from both T Iand
the pure dephasing time T,’, and it is the latter process, which arises from differences
in the scattering amplitudes between the ground and excited states, which is the
origin of the temperature dependence. Apart from identifying the two dephasing
mechanisms the study also showed that the decay of the primary state was not
sensitive to the bandwidth or correlation time of the different excitation sources
used. This is an interesting paper and serves as a good example of the application of
optical-coherence techniques in chemical physics for readers unfamiliar with such
work.
The photophysical properties of N-heterocyclics are strongly influenced by the
close proximity of nli‘ and mP excited states. A series of experimental investig-
ations (see reference 367 and others reported below) has shown that the rate of
radiationless decay from both the first excited singlet and triplet states increases as
the energy gap between their respective nli‘ and n.lr*states decreases. The results of
quantum statistical mechanical calculations of vibronic coupling between the two
states and its effect on the radiationless decay rate, using simple harmonic potentials
for the states, were found to be consistent with the experimental results and to
support the idea that vibronically active out-of-plane modes are the dominant
accepting modes for such processes in N-heterocyclics with close-lying nli’ and mP
excited states.372A useful discussion of the meaning of the term vibronic coupling
has been published; it carefully considers the various adiabatic approximations and
their different terminologies found in the literature and the various approaches to
obtain exact wavefunctions by making corrections to the adiabatic approxim-
ations.373The framework for the discussion is shown in Figure 17. The analysis
shows that the term ‘vibronic coupling’ is used in the literature to indicate the
general concept of corrections to certain kinds of inexact wavefunctions. A paper
has critically examined two features of theories of radiationless processes in
molecules, namely the assumption that the initially prepared state in an adiabatic
Born-Oppenheimer (ABO) state and the procedure used to evaluate off-diagonal
matrix elements of the nuclear kinetic-energy operator.374 A model of three
electronic states is considered in which the two excited states are coupled through
the same non-totally-symmetric mode that couples the lower excited state and the
ground state. Strong non-adiabatic mixing effects were found to occur when levels
of the two excited states were in resonance, and this results in ‘anomalous’
behaviour in the energy-gap law, i.e. instead of decreasing exponentially with an
increasing energy gap the radiationless decay rate between the excited and ground
states may actually increase. The results support a description of internal
conversion processes in terms of non-adiabatic transitions between two electronic
ABO manifolds and also lead to a new method involving numerical integration for
calculating the appropriate non-adiabatic matrix elements. Previously used
372 W. A. Wassam, jun. and E. C. Lirn, J . Chem. Phys., 1978, 68, 433.
373 T. Azumi and K . Matsuzaki, Photochem. Photobiol., 1977, 25, 315.
374 A. P. Penner, W. Siebrand, and M. Z . Zgierski, J . Chem. Phys., 1978, 69, 5496.
62 Photochemistry
methods for calculating the latter were shown to give results in error by several
orders of magnitude. It has been observed experimentally that radiationless decay
rates in isolated molecules depend on the rotational state of the molecule. The
LY-.
Figure 17 Various routes to approach the exact non-adiabatic wavefunction

(Reproduced with permission from Photochem. Photobiol., 1977, 25, 215)
rotational matrix elements and selection rules for internal conversion processes
between two singlet states and two triplet states and for intersystem crossing
between a singlet and a triplet state have been The study considers
polyatomic molecules in Hund’s case4 angular momentum coupling scheme in
which N , K , J , and S are the good quantum numbers, and the results indicate that
the selection rules depend on both the angular-momentum coupling and the
interaction operator. It has been demonstrated experimentally that a magnetic field
quenches the fluorescence of I 2, CS,, glyoxal, and NO, molecules in the gas phase.
A general treatment of the effect of magnetic fields on radiationless transitions has
been published. 3 7 6 It identifies three mechanisms as possibly contributing to the
observed quenching: ( i )a direct mechanism, in which an existing zero-field coupling
element between a prepared state and an adjacent quasi-continuum is enhanced by
a Zeeman term and which, since the states must be of favourable symmetry and of
the same spin, applies only to internal conversion, (ii) an indirect mechanism, in
which the Zeeman interaction causes a change in the existing coupling, involving
perhaps an intermediate state, and may affect both intersystem crossing and
internal conversion (unlike the direct mechanism, which increases the rate of the
375 W. E. Howard and E. W. Schlag, J . Chem. Phys., 1978, 68, 2679.
376 P. R . Stannard, J . Chem. Phys., 1978, 68, 3932.
radiationless decay quadratically in the field, the indirect mechanism leads to a
quadratic dependence on the field at low fields, as in the direct mechanism, but to a
constant value at high fields), and (iii) a mechanism arising from a simple level-
shifting effect, which may bring about different resonances but which is only
expected to be noticeable for intermediate case molecules. The paper discusses each
of the specific cases mentioned above. A general model for discussing the
radiationless decay of a polyatomic molecule is of an initially prepared isolated
state strongly coupled to a manifold of intermediate states that in turn are strongly
coupled to a continuum of final states representing dissociation and/or vibrational
relaxation. A paper has discussed the case where there is a random coupling
between the levels that is subject to two weak perturbations, a constant coupling or
a Lorentzian coupling, the latter being appropriate for vibrational relaxation in
The time evolution of the initially excited vibrational mode in the
Lorentzian coupling-random coupling case exhibits two time constants at short
times, one of which corresponds to a redistribution of energy amongst nearly
resonant modes and the other to the relaxation to lower-lying modes.
A discussion by Birks of so-called horizontal radiationless transitions (HRT) in
stilbene and polyene derivatives has resulted in a classification of five types of
behaviour for the S , and S , potentials on rotation about a central double bond. 378
HRTs alter the steric configuration of an electronic state and also its zero-point
energy and sometimes its wavefunction and symmetry. They also change the energy
separation between the state and adjacent states. The discussion is based on a semi-
empirical model of the potential surfaces of the ‘B* and ‘A* excited singlet states
which interact because of asymmetric perturbations, probably torsional vibrations
excited by collisions, distorting the otherwise non-interacting (because they have
different symmetry) surfaces. The five types of potential are illustrated in Figure 18.
A new approach to the calculation of intramolecular radiationless transitions
called the non-integral occupation number (NION) method has been described. 379
The new approach departs from other methods based on the golden-rule expression
of time-dependent perturbation theory by avoiding both the usual generating-
function evaluation of a sum in the vibrational quantum numbers n, in the final
electronic statefand the saddle-point approximation to evaluate the 1’ d t integral
which arises from the &function. The final expression for the radiationless decay
rate from an initial electronic state i with rn quanta in the first vibrational degree of
freedom is given by equation (1 5), where w 2 is the frequency of the best accepting
mode 2, Bvis the electronic factor, and y is a non-integral measure of the number of
available 2-quanta in the final state. The important term is the NION
Franck-Condon factor 1 ( 0 I n, ) In, = y, and this emphasizes the importance of
the accepting mode in this simple method, which is shown to subsume many
previous methods. A series of model calculations of relative rates, R,Xrn, # 0,
m3 # O)/R&rn, = 0 = m3), are presented for the S1 + T , , ISC, and S1--* So,
3’7
M . Muthukurnar and S. A. Rice, J . Chem. Phys., 1978, 69, 1619.
378 J. B. Birks, Chem. Phy.y. Lett., 1978, 54, 430.
379 I. H. Kuehn, D. F. Heller, and W. M. Gelbart, Chem. Phys., 1977, 22, 435.
64 Photochemistry
IC, processes in benzene to investigate the competing effects of anharmonicity,
geometry changes, and frequency shifts in all the relevant vibrations. It is clearly
shown that all of these effects must be considered to obtain a realistic picture of the
iiiil
-
t y x z
C 0 WF I G UR A l l 0 N
p
Figure 18 Schematic diagrams of the angular dependence of the S and S2potentials between t
and p. A = 'A*, B = 'B*
molecular structure parameters that are important to the decay process. It is argued
that the failure of the model to account for the observed increase in relative rates for
the S , + So process arises from the assumption in the golden-rule expression that
the interaction energy may be written as a product of an electronic factor and a
vibrational overlap integral. This requires modification when potential surfaces
interact, as is the case for 'channel 3' which appears ~ 3 0 0 0 c m - above the origin
of the first excited singlet state.
The effect of introducing unequal quasi-continuum couplings into the well
known Bixon-Jortner model of radiationless processes has been discussed.380 The
paper argues for a new approach in which the lack of quasi-continuum matrix-
380 S. D. Druger, Chem. Phys. Lett., 1977, 48, 46.
element correlation is introduced at the outset and which can avoid a number of
qualitative effects implied by the Bixon-Jortner model that are not observed
experimentally. Conditions under which a non-Markovian radiationless decay
process exhibits a rigorous exponential behaviour have been investigated. 381 Such
decays are shown to result from both a finite excitation pulse fall time and a
transverse relaxation process. An expression for the ratio of radiative to non-
radiative decay in electronically excited solid-state materials has been
developed. 3 8 2
The tunnel-effect theory or radiationless transitions described in my previous
contribution to this series (see ‘Photochemistry’, Volume 9) has been extended to
study substituent effects on intra- and inter-molecular H-abstractions of carbonyl
excited electronic states. 3 8 3 The results have revealed that photoabstractions by
n,n* singlet and triplet states and n,n* triplet states are adiabatic processes, whereas
photoabstractions by singlet n,n* levels have an electronic forbidden factor of
< 10- 2. It is shown that these observations are consistent with the state correlation
diagrams of Salem. The possible role of a charge-transfer process in intramolecular
H-abstractions is also discussed in the paper, and such a process is viewed as one
extreme, the other being radical-like abstractions, of a mechanistic continuum for
photoabstraction reactions. The application of the tunnel-effect theory has also
been investigated in a study of hydrogen-abstraction reactions by triplet n7ZC
benzophenone. 3 8 4 The theory was able to predict successfully the quenching rate
constants of NN-dimethylaniline and triethylaniline as substrates, but for the cases
of n-hexylamine and isopropylamine the agreement was not so good. The origins of
the discrepancies are discussed, and in particular the difficulty of obtaining
adequate potential-energy surfaces is pointed out. In its simplest form the theory
uses the harmonic-oscillator approximation to calculate both D,the energy barrier,
and Ax, the barrier width. The nature of the energy barrier in such reactions has also
been the subject of a more recent paper.385
Intersystem Crossing. A Green’s function technique has been used to formulate an
expression for S --* T intersystem crossings (ISCs) in aromatic hydrocarbons.3 8 6
There are a number of outstanding questions concerning the ISC process in such
molecules, including benzene itself, such as the identity of the promoting modes,
which have not been resolved by recent experimental and theoretical work. Using a
pure-spin Born-Oppenheimer basis set, an expression for the ISC rate constant is
derived which involves diagonal terms of both spin-orbit coupling and non-
adiabatically induced spin-orbit coupling and also cross terms between them which
are usually neglected. Such a mechanism leads to a classification of promoting
modes into two groups. The first group is determined by the condition that the
vibronic spin-orbit coupling matrix element must not vanish and the second by a
similar condition for the vibronic coupling matrix elements which involve the
nuclear momentum operator. An approximate calculation of the former for the
38’ P. Grigolini, Chem. Phys. Lett., 1978, 58, 185.
382 A. M . Stoneham and R. H . Bartram, Solid-Slate Elecrron.. 1978, 21, 1325.
383 S. J . Formosinho, J . Chem. Soc.. Faraday Trans. 2 , 1978, 74, 1978.
384 G. D. Abbott and D. Phillips, Mol. Photochem., 1977, 8, 289.
385 H . Cardy, E. Poquet, M . Chaillet, and A. Dargelos, N o w . J . Chim., 1978, 2, 603.
38h Y. Fujimura, N. Simakura, and T. Nakajima, J . Chem. Phys., 1977, 66, 3530.
66 Photochemistry
S, ( ’B,) -+ T1X*Y(3Blu) ISC process in benzene indicates that the dominant
promoting mode is the elg C-H out-of-plane vibration (vl0), and this is true for
both a direct S , - T , and an indirect S , -+ T , T , mechanism. High-resolution
-+
measurements of naphthalene fluorescence in the collision-free low-pressure region

have revealed a strong rotational effect on the quantum yield within a single
vibronic The effect was shown to be present in both the measured radiative
and non-radiative rates; however, in the case of the radiative rate constant it was
shown, using a Master equation approach, that ensemble averaging can make a
constant microscopic radiative rate constant appear to vary. In the case of the non-
radiative rate constant the authors developed a theory of rotationally selected ISC
rate constants which they have more recently used to calculate features of the
rotational contours of two vibronic bands of [ ‘HJnaphthalene. The rotational
structure was shown to depend on the rotational distribution, the electronic
spin-orbit matrix elements, the promoting mode energy, the Franck-Condon
weighted density of states, and a rotational term involving the Wigner 3-J symbols.
The rates of the ISC processes from the lowest triplet state of molecular dimers
compared with those from the lowest triplet state of the separated molecule have
been derived. 389 The results, in combination with ZFS data, can be used in studies
of the structures of such pairs. Ab initio CI calculations of molecular wavefunctions
in pyrazine, using minimal basis sets of Gaussian atomic orbitals, have resulted in
estimates of the singlet-triplet spin-orbit matrix elements in this molecule. 390 The
calculated radiative lifetime of the short-lived component, i.e. the y component, of
the lowest triplet state 3B3uwas in good agreement with the experimental value,
giving confidence to the general approach taken in the paper. The results indicate
that the strongest interactions in both the T , + So and S , -B T , ISC processes
involve the ry
spin component.
Although it is an intermolecular effect (an energy-transfer process) a few
interesting papers on collision-induced intersystem crossing are reported on in this
section. As summarized in the first of these-papers 3 9 1 the experimental observ-
ations of this process in ‘intermediate case’ molecules such as glyoxal are as follows:
(a) the systems exhibit a strong fluorescence self-quenching effect,
(b) the quenching effect is markedly dependent on the particular vibronic state,
(c) the triplet yield is anomalously high, and
(d) the pressure dependence of the fluorescence yield is complex.
A general theory is developed in which the effect is attributed to a resonant Sjil -,
TkP2 transition, where 1 and 2 distinguish the two molecules involved, j and k are
the electronic states, and i and p are the vibrational levels. The rate of energy
transfer at a separation R is given by equation (1 6), where p represents the levels
that are in resonance, V,,, the corresponding coupling between the levels, and y the
natural width of the resonance. After appropriate averaging of the ‘collision’
’” W. E. Howard and E. W. Schlag, Chem. Phys., 1976, 17, 123.
’” W . E. Howard and E. W. Schlag, Chem. Phys., 1978, 29, 1.
389 M . K . Bowman and J. R . Norris, Chem. Phys. Lett., 1978, 54, 45.
390
G. L. Bendazzoli, G. Orlandi, and P. Palmieri, J . Chem. Phys., 1977, 67, 1948.
391 R. Naaman, V. Yakhot, and G. Fischer, J . Chem. Phys., 1977, 67, 5472.
trajectories the emission intensity at low pressures, I , is given by the expression
I = I,exp ( - PP)”~, where p is the pressure and /3 a constant derived from the
molecular properties and the temperature. This strong pressure dependence of I at
low pressures predicted by the theory was found to agree quite well with
experimental observations in quinoxaline and benzophenone. At high pressures
other mechanisms, not included in the theory, will contribute to the energy-transfer
behaviour. A comprehensive theory of collision-induced intersystem crossing has
been extended to include the effect of individual collision trajectories on the cross-
section for the process.392The work was prompted by recent experimental work on
inert-gas quenching of CO fluorescence, which indicated that the cross-section, 0,
for the process was not linearly dependent on the average value of the singlet-triplet
mixing coefficient, x2.393 In contrast to the resonant transition model above, the
‘collision’is regarded as a perturbation of an intramolecular radiationless process.
The new model considers both weak long-range attractive and short-range
repulsive interactions, and collisions are divided into two categories. In the first of
these the internal-energy transfer is large compared with the interaction energy, and
this results in the linear dependence of d o n x 2predicted by the earlier theory. In the
second category, called perturbed mixing collisions, where the energy transfer is
comparable to the interaction energy, a non-linear dependence of u on x 2 was
predicted. A model of collision-induced intersystem crossing involving the
formation of a collision complex has been applied to polyatomic molecules such as
glyoxal. 394
Of the numerous experimental investigations of ISC processes only a few
representative examples will be reported here. An extensive review (in Polish) of the
experimental methods for the determination of S , + T , ISC quantum yields has
been published,395and this was followed up by the same authors with a review of
the physicochemical factors which determine these yields. 396 A strong red emission
observed on excitation of Ca atoms in a solid Ar matrix originates from the 4p 3P
state and is evidence for an efficient spin-forbidden non-radiative multiphonon
relaxation process.397This observation is consistent with recent work by the same
author on small molecular guests in rare-gas solids. Detailed studies of the
phosphorescence lifetime and yield of [’ H6]- and [2H6]-benZenein glassy and
crystalline media at low temperatures (2-30K) have revealed that both the
radiative and non-radiative decays originate from the nearly degenerate upper pair
of spin sublevels, E , = D - E and Ex = D + The observed temperature-
dependent behaviour could be explained entirely by the combined effects of a
Boltzmann population term and a spin-lattice relaxation term. The ISC rate
constants of a number of aromatic ketones have been measured directly by
following the build-up of the triplet-state absorption using picosecond-laser
spectroscopy techniques. 399 Similar values were found for benzophenone, an-
392 K. F. Freed and C. Tric, Chem. Phys., 1978, 33, 249.
393 D.Grimbert, M. Lavolee, A. Nitzan, and A. Tramer, Chem. Phys. Lett., 1978, 57, 45.
394 H . L. Selzle, S, H . Lin, and E. W. Schlag, Chem. Phys. Lett., 1979, 62,230.
395 B. Matuszewski and A. Maciejewski, Wiad. Chem., 1977, 31,791.
39b A. Maciejewski and B. Matuszewski, Wiad Chem., 1978, 32, 151.
39’ V. E. Bondybey, J . Chem. Phys., 1978, 68, 1308.
398 N. G. Kilmer and A. H. Kalantar, Chem. Phys., 1978, 27, 3 5 5 .
399 D. E. Damschen, C. D. Merritt, D. L. Perry, G. W. Scott, and L. D. Talley, J . Phys. Chem., 1978,82,
2268.
68 Photochemistry
throne, xanthone, and a number of para-substituted benzophenones. The quantum
yields of T , + S , ISC processes in anthracene and a number of its derivatives have
been measured by a double-excitation method.400 The failure of the simple
logarithmic energy-gap law for k,,, when the energy gap I AE(S,-T2) I is small has
been investigated experimentally and theoretically for a number of 9,lO-substituted
anthracenes. 401 The widely different photophysical properties in these compounds
are attributed to interference effects between the S , + T , and S, + T , ISC
processes. The triplet build-ups observed in a picosecond-laser spectroscopic study
of several carbonyl derivatives of anthracene have been attributed to the
T,, + T I E ,IC process and not to the SIEn. T,,, ISC process which precedes
it.402The latter process was thought to be significantly faster than the former rate-
determining step.
Non-radiative decay processes in the azabenzenes, pyridine, pyrazine, and
pyrimidine have been investigated using an intermolecular triplet-triplet energy
transfer to b i a ~ e t y l . ~The
’ ~ results have revealed a new non-radiative decay channel
in the S,(’nn*) state ofboth [‘H5]- and [2H5]-pyridine,1000cm-’ above the lowest
vibrational level, and similarly for pyrazine and pyrimidine in the 3000cm-
excess-energy region. The influence of the proximity effect between a coupled pair
of nlir and nlir states, which was mentioned earlier in this section, on the T , + S o
ISC process in pyrazine and two of its methyl derivatives has been discussed.404
The electronic-energy gap between the triplet nlir and nlir states is modified by
substitution, and the results show that as this gap decreases the radiationless decay
rate increases. The corresponding increase in the vibronic coupling is evidenced by
the increasing out-of-plane activity in the phosphorescence spectra. ODMR
methods have been used to investigate the S , * T , ISC process in ~yrimidine.~”
An anomalously high z, spin sublevel population rate (x is the out-of-plane axis)
observed in an earlier study of pyrimidine in a benzene matrix was shown to
disappear if a 5-methylpyrimidine matrix was used. The effect can be attributed to a
pseudo-Jahn-Teller distortion of 3A,( ZIP) and/or 3B2(nlir) potential surfaces by a
higher-lying 3A (nlir) state. An energy-level diagram for pyrimidine that shows
this ordering and a number of other features is shown in Figure 19. An experiment
in which the triplet state of [2H12]-tetramethylpyrazine in durene at low temperature
is produced following a short duration laser excitation at 266nm has proved that
the S , + T , ISC process results in a non-stationary superposition of two zero-field
spin states which is coherent throughout the ensemble. 406 The effect manifests itself
as a microwave free-induction-decay signal at the resonant frequency of the ~ ~ - 7 ~
transition. A study of the S , + T I ISC process in acridine in PVA film has
suggested that two processes are involved.407 The first is a temperature-dependent
process which proceeds via T,(n,n*) to T , ( ~ , l i r and ) , the second i s temperature-
400 s. Kobayashi, K. Kikuchi, and H. Kokubun, Chem. Phys., 1978,27, 399.

40’
C. Jung and K. H. Heckner, Chem. Phys., 1977, 21, 227.
402 S. Hirayama and T. Kobayashi, Chem. Phys. Letr., 1977, 52, 55.
403 K. Aizawa, H . Igarashi, and K . Kaya, Chem. Phys., 1977, 23, 273.
404 S. L. Madej, G . D. Gillespie, and E. C. Lim, Chem. Phys.. 1978,32, 1.
405 A . Inoue and E. C. Lim, Chem. Phys. Lett., 1979,62, 250.
406 C. J . Nonhof, F. L. Plantenga, J. Schmidt, C. A. G . 0.Varma, and J. H. Van der Waals, Chem. Phys.
Lefr., 1979, 60,353.
407 K. Kikuchi, K . Ujue, Y. Mujashita, and H. Kokubun, Buff.Chem. SOC.Jpn.. 1977, 50, 879.
independent and proceeds via T2(n,7P)to Tl(n,n*). The role of the singlet n,lr* state
in this process is discussed in a study of acridine triplet quantum yields in a variety
of solvents.408The effect of T , formation in acridine and phenazine vapours has
1
A , (*no) -
G -
Figure 19 The low-lying electronic states of pyrimidine. The spin-orbital symmetries are
indicated in parentheses
been studied by a flash-photolysis technique.409 The general dependence was in

strong contrast to that previously observed for anthracene. The pressure effects
were attributed to a reversible ISC process.
A Raman laser temperature-jump system has been used in a study of ISC
processes in solution for six-co-ordinate dS, d6, and d7 spin equilibrium metal
complexes of iron(m), iron(II), and cobalt(~r).~lA consistent picture of the
observed rates is given by a model which treats the spin multiplicity change as an
internal electron transfer. The influence of a solvent relaxation process on the
4T2+ *Eprocess in tris(ethylenediamine)chromium(Irr) has been noted in a laser-
photolysis study of this system in water-glycerol mixtures. 4 1 '
A careful study of internal heavy-atom effects on the triplet lifetimes of the eight
monohalonaphthalenes (4 different halogens and 2 inequivalent positions) and ten
monohalophenanthrenes were measured, and the results show that for a particular
substitution site the total decay rate is proportional to the square of the spin-orbit
coupling factor of the substituted halogen and that for a particular halogen there
408 K . Ujiie, K. Kasama, K . Likuchi, and H. Kokubun, Chem. Lerr., 1978, 247.
4"9 J. L. Baptista, S. J . Formosinho, and F. Leitao, Chem. Phys., 1978, 28, 425.
410 E. V. Dose, M . A. Hoselton, N . Sutin, M . F. Tweedle, and L. J . Wilson, J . Am. Chem. Soc., 1978,100,
1141.
41' C. Conti, F. Castelli, and L. S. Forster, Inorg. Chim. A m , 1979, 33, L171.
70 Photochemistry
are clear substitution-position effects.4 1 * In the latter effect the phosphorescence
lifetimes of 2-substituted naphthalenes were found to be longer than 1-substituted
derivatives by between 4 and 14%, depending on the halogen, and in the case of
phenanthrenes the lifetimes were found to be in the order 2-Br > 1-Br > 3-
Br > 4-Br > 9-Br, as exemplified by the bromo derivatives, there being a lifetime
difference of a factor of nearly 20 between the longest and the shortest. The internal
heavy-atom effect on the individual spin sublevel decay constants of halo-
naphthalene triplet states has been measured and reveals that it is most prominent
for the z, and z, sublevels (the x- and y-axes being the long and the short axes,
respectively, in the plane of the molecule), a result consistent with a model involving
a spin-orbit coupling mechanism.413A study of 2-halo- and 1,3-dihalo-azulenes
has revealed a clear heavy-atom effect on the radiationless decay processes in these
molecules, supporting the idea that an ISC process must be included in a decay
scheme as well as an S , + S , internal conversion p r o ~ e s s . ~ l ~interesting
An study
of the effect of the substitution of heavy atoms in the aryl group of 6-N-arylamino-
2-naphthalene sulphonate (6,2-ANS) has provided more evidence in support of a
model of the photophysical properties of this molecule which may be summarized
as in Scheme 1, where np denotes naphthalene-like emission which is only weakly
Scheme 1
dependent on solvent polarity and where ct denotes a charge-transfer emission

which involves both the N-aryl group and the naphthalene ring and is sensitive to
the solvent polarity.415The heavy-atom substitution was found to reduce the np-
type fluorescence-emissionquantum yield but not to affect the yield from the ct-type
state. Heavy-atom effects on the decay processes of electronically excited
manganese@) ion in solutions have been investigated using different anions (Cl- ,
Br-, and I-) and a range of solvents.416
Inter- and intra-molecular heavy-atom effects on the triplet-state decay para-
meters of naphthalene and quinoline have been investigated using a phosphor-
escence microwave double-resonance (PMDR) method,41 and a study of meso-
substituted anthracenes has revealed a single linear correlation between the
activation energy for the S , --+ TISC process and the logarithm of the fluorescence
quenching rate constant by halo alkane^.^'^ Apparently in the latter study both
processes have the same dependence on the energy-level difference between S , and
the accepting triplet level T,. The external heavy-atom effects of silver (AgNO,) on
'Iz J. C. Miller, J. S. Meek, and S. J . Strickler, J . Am. Chem. Soc., 1977, 99, 8175.
4'3 H. Saigusa and T. Azumi, J . Lumin., 1979, 18/19, 187.
414 G. Eber, S. Schneider, and F. Eoerr, Chem. Phys. Lett., 1977, 52, 59.
415 E. M. Kosower and H. Doduik, J . Phys. Chem., 1978, 82, 2012.
4'6 S. P. Naumov and E. B. Sveshnikova, Opt. Spektrosk., 1978, 45, 903.
417 K. J. Latas and A. M. Nishimura, J . Am. Chem. Soc., 1978, 82, 491.
418 H. Dreeskamp and J. Pabst, Chem. Phys. Lett., 1979, 61, 262.
the luminescence of aza-aromatics and carbazoles 4 1 9 and of barium(r1) on the
fluorescence of naphthalene 4 2 0 have both been investigated.
Internal Conversion. An examination of a number of frequently used approxim-
ations in the calculation of non-radiative matrix elements involving the nuclear
kinetic-energy operator has shown that they can lead to large errors.421Exact
expressions for the matrix element of a simple model involving adiabatic potentials
are derived, and calculated values are compared with those obtained using both an
approximate solution that is equivalent to first-order Tanaka-Fukuda perturb-
ation theory and a solution that uses the spectroscopic Herzberg-Teller procedure
based on the Condon approximation. Except for the use of the latter procedure far
from resonance and for small quantum numbers, both approximations are shown
to be inadequate. The important conclusion reached is that radiationless transitions
do not involve spectroscopic Franck-Condon factors. A new form for the
vibrational integrals is given which results in a generally increased value for
calculated matrix elements compared with Franck-Condon-based formulae,
thereby improving the agreement with experiment. An interesting ab initio CI
calculation of the radiationless decay of the l(nn*)state of formaldehyde has been
An adiabatic Born-Oppenheimer basis set is used in the calculation
of this S , --+ So internal conversion (IC) process, and following an analysis of the
possible couplings between levels in the initial ' A 2 and final ' A , states it is shown
that both H 2 C 0 and D,CO are examples of the so-called resonance case in which
the density of coupling levels is so low that any interaction arises from a fortuitous
position of the interacting levels. The contribution from rotational coupling terms
which can be treated along with vibrational coupling terms in the method used was
shown to be negligible. The results show that contrary to earlier proposals this IC
process is not the rate-determining step in the photodissociation of formaldehyde.
It is also shown that a previous calculation of the rate of this S , + SoIC process
was based on a golden-rule rate expression derived from time-dependent perturb-
ation theory which can be shown to lead to inconsistent results. A discussion of IC
processes in aromatic molecules has included a discussion of the theoretical basis
and range of applicability of Kasha's rule.422 Theoretical calculations of the
S1+ SoIC process in electron donor-acceptor complexes of tetracyanoethylene
with aromatic hydrocarbon donors using a many-promoting-modes model were
found to be in good agreement with experimental values.423
Of the numerous experimental studies of IC processes only a few are mentioned
here. A study of the so-called 'a-substitution effect' has indicated that the ability of
t-butyl groups to facilitate aryl S , --+ So IC processes may be a general pheno-
m e n ~ n . ~An , ~interesting study of the energy andisotope dependence of the
S , + S , and S , + So IC processes in azulene under collision-free conditions has
been The results show that the S , + So IC process is in competition
419 M . Zander, Z . Naturforsch., Teil A , 1978, 33, 998.
'lo A. M. P. C. De Amorim, H. D . Burrows, and S. J. Formosinho, Spectrochim. Actu, Part A , 1977,33,
245.
42' W. Siebrand and M. Z. Zgierski, Chem. Phys. Lett., 1978, 58, 8.
421 V. G. Plotnikov and B. A. Dolgikh, Opt. Spektrosk., 1977, 43, 882.
423 J. Prcchorow, I. Deperasinska, and A. Sobelewski, J . Lumin., 1977, 18/19, 105.
424 W. W. Schloman, jun. and H . Morrison, J . Am. Chem. Soc., 1977, 99, 3342.
425 Y. Hirata and E. C. Lim, J . Chem. Phys., 1978, 69, 3292.
72 Photochemistry
with the S , + So process and may be the dominant decay process even at zero
excess energy. Its rate is every bit as anomalous as the S , -+ So process with respect
to the ‘energy-gap law’ for IC processes in aromatic hydrocarbons in that they are
both several orders of magnitude greater than the predicted value. The results
support the idea that the geometrical structures of the S, and S, electronic states are
similar and that both the IC processes to the ground electronic state involve large
configurational changes. A study of the energy dependence of the luminescence of
quinoline and isoquinoline vapours has been interpreted in terms of the dominance
of an S, -, So IC process from vibrationally excited S,.426This phenomenon is
thought to be general for nitrogen-heterocyclic compounds with closely spaced,
lowest-energy nn* and nn* states. The results indicate that the S2(nn*) + Sl(nn*)
IC process is collisionally induced for low vibrational levels of S2 but that it is an
efficient process, characteristic of the statistical limit, for higher vibrational levels of
S,. The S , -,S , IC process in biacetyl in both the liquid and the vapour phases has
been investigated.427
Vibrational Relaxation. A valuable and interesting review of the theoretical
background and experimental results of studies of the vibrational dynamics of
liquids and solids in their ground electronic states using picosecond-laser pulses has
been The paper discusses the stimulated Raman scattering and
infrared-absorption excitation processes and the coherent and incoherent Raman
scattering and fluorescenceprobing processes used in such studies. The first of these
probing techniques, coherent Raman scattering, has been used in conjunction with
stimulated Raman excitation to give information on the dephasing time T, of
excited modes both in molecules with essentially only one vibrational frequency or
in more complex situations, to observe the collective beating of neighbouring
frequency components, and to measure the lifetime of optical phonons in crystals.
The second two probing techniques have been used to observe directly population
lifetimes, also energy transfer and redistribution processes in the liquid state with
time constants in the range 1-100 ps. A new technique for measuring vibrational
relaxation times, called coherent Raman induced infrared fluorescence (CRIIF),
has been described in the literature and applied in a representative study to the
D,-HCl In the technique a Raman transition with frequency (wL - ws)
is excited by simultaneously exposing the sample to a pumping frequency wL and a
Stokes frequency ws. The transfer of excitation from the totally symmetric states so
produced to dipolar states can be followed by observing the risetime and decay of
the i.r. fluorescence. Another laser-induced fluorescence method is illustrated by a
study of CH3F, in which fluorescence from the overtone 2v3 of the C-F stretch
vibration is measured following excitation at the fundamental frequency v3.430 The
v3 and 2v3 are tightly coupled, and any decay of 2v3 fluorescence is a measure of v3
transfer to other modes. Laser-induced fluorescence techniques have been used to
42h S. Okajima and E. C. Lim, J . Chem. Phys.. 1978, 69, 1929.

42’ C. Richard, M. Bouchy, J. C. Andre, and M. Niclause, Int. J . Chem. Kinet., 1978, 10, 213.
428 A . Laubereau and W. Kaiser, Rev. Mod. Phys., 1978, 50, 607.
429 A . D. Devir and S. H. Bauer, J . Chem. Phys., 1978, 69, 2682.
430 R. S. Sheorey, R. C. Slater, and G . W. Flynn, J . Chem. Phys., 1978, 68, 1058.
431 J. M. Wiesenfeld and C. Bradley Moore, J . Chem. Phys., 1979, 70, 930.
measure the vibrational relaxation of HCl and DCl,431 H, 180,432 and BaO
(X'C+),433the latter being produced by reacting Ba atoms with 0, in a jet flow.
A notable paper on the mode-to-mode vibrational-energy flow in the first excited
singlet state, 'Bz,, of benzene has been published.434 The measurement of high-
resolution fluorescence spectra following excitation into the 6 ' ( v ' , = 1) level at
522 cm - under 'single-collision' conditions in low-pressure mixtures of benzene
and a number of added gases has made it possible to identify the energy flow into
four specific channels. This process is represented in Figure 20, which shows that
two of the channels are to single levels and the other two channels involve two final
-7 11'
400
20:l
-285
16'
1
-522
00
Figure 20 A schematic showing every vibrational level up to 1200 cm- above the zero-point
level in S , benzene. The arrows show the vibrational-energyflow monitored in these experiments.
The level 6 , is initiallypumped, and collisional transfer into each of thefour channels A through
D is monitored. Two channels characterize$ow to single levels (ignoring degeneracies). The
other channels involve twofinal levels. The energy separation between 6' and thefinal levels is
given in cm- '. Many levels are instrinsically degenerate; these components have not been
depicted. Heavy lines in the level stack indicate level pairs too close to show individually
(Reproduction with permission from Chem. Phys., 1978, 27, 127)
levels. These four channels account for over 70% of the total energy flow despite the
large number of energy levels in the same energy region, and clearly this indicates
that strong propensity rules are operating. It was found that simple rules previously
derived to described vibrational relaxation in ground electronic states in poly-
atomic molecules can be successfully applied to the S, benzene state. The rules are
based on an expression for the transfer probability which is a product of terms
involving the level degeneracies, the change in the vibrational quantum number,
and the amount of energy exchanged between vibrational and
translational/rotational degrees of freedom. The cross-sections for vibrational-
energy transfer were found to be significantly larger in the excited electronic state
(approaching gas kinetic) compared with those for ground states, in agreement with
432 J . Finzi, F. E. Hovis, V. N . Panfilov, P. Hess, and C. Bradley Moore, J . Chem. Phys., 1977,67,4053.
433 S . A. Edelstein, B. E. Perry, D. J. Eckstrom, and T. F. Gallagher, Chem. Phys. Lett., 1977,50, 271.
434 C. S. Parmenter and K . Y. Tang, Chem. Phys., 1978, 27, 127.
74 Photochemistry
previous observations and possibly arising from stronger long-range attractive
forces between excited states and other molecules. The existence of propensity rules
in other systems is supported by a recently published study of vibrational-energy
flow from eight vibronic levels in the ’B2 state of aniline in which argon is the
collision partner.435The study, which differs from that on benzene in that intensity-
versus-time measurements are also used in addition to steady-state measurements to
verify the kinetic model used in the analysis, does, however, indicate that the
propensity rules as presently stated are inadequate. In both the aniline and benzene
studies it was observed that a dominant channel for vibrational-energy transfer was
to a higher-energy vibrational state, and this had led to the suggestion that this
channel involves the formation of a metastable intermediate.
A study of vibrational relaxation in the B,, state Of p-F2C6H4 has shown that
unlike a previous study of p-FC6H4Me the stochastic stepladder model does not
account for the observed fluorescence quantum yield and lifetime results.436In this
simplified model the molecule has only one effective oscillator, and the decay rates
from its levels are a linear function of the level number n. It is further assumed that
collisions only induce transitions from state n + 1 to state n. The authors suggest
that for the model to apply there should be a high density of initially populated
levels. Preliminary results from a study of the fluorescence excitation spectrum of
supercooled naphthalene in a pulsed supersonic molecular beam show a trend of
increased broadening, the higher the vibrational energy.437
The Singlet State.-Resonance Fluorescence. There continues to be a great deal of
interest in the experimental and theoretical aspects of the resonance fluorescence of
atoms and molecules in intense monochromatic or finite bandwidth radiation fields.
The character of the fluorescence emission changes considerably on going from low
to high intensity radiation. The fluorescence spectrum, for example, changes from
purely monochromatic at low intensity to exhibit complex structure at high
intensity. A new approach to the theoretical description of resonance fluorescence
has been published which has a number of advantages over existing treatments.438
In the dressed-atom approach resonance fluorescence is considered as spontaneous
emission from the system comprising the atom and the laser mode, i.e. the atom
dressed by laser photons. A simple procedure, illustrated for the case of a two-level
atom, shows that the components of the resonance fluorescence spectrum are the
allowed Bohr frequencies of the dressed atom. A number of other properties are
also readily obtained, and the authors point out that the approach is well suited to
the treatment of multilevel systems and the effects of collisions and of Doppler
shifts. There has been further discussion of the effect of using finite bandwidth
excitation to excite resonance fluorescence.439A theoretical treatment has shown
that in contrast to truly ‘monochromatic excitation a pronounced asymmetry
appears in the resonance fluorescence when using off-resonance excitation with
435 D. A. Chernoff and S. A. Rice, J . Chem. Phys., 1979, 70, 2521.

43h R . P. Steer, M. D. Swords, and D. Phillips, Chem. Phys., 1978, 34,95.
43’ S. M. Beck, D. L. Monts, M. G . Liverman, and R. E. Smalley, J . Chem. Phys., 1979, 70, 2062.
438 ( n ) C. Cohen-Tannoudji and S. Reynaud, J . Phys. B, 1977, 10, 345; (b) C. Cohen-Tannoudji and S.
Reynaud in ‘Multiphoton Processes, Proc. Int. Conf. 1977’, ed. J. H. Eberly and P. Larnbropoulos,
Wiley, New York, 1978, p. 103.
439 L. Mandel and H . J . Kemble in reference 4386, p. 119.
finite bandwidth radiation. This effect is illustrated in Figure 21. Resonance
fluorescence from a two-level atom has been treated as an example of non-
equilibrium thermodynamics in a quantum system in which there is a coherent
Frequency W - ~ I in ) units of 13
~ ~r ) 2 / ( o o 2,u sin$)2 of thefluorescence radiated by a driven
Figure 21 Spectrum CP ( a ) ( 4 l l C2
atom in the steady state,for various values of the excitation bandwidth I , with Rabifrequency
R = log, and detuning 0 = - 3
(Reproduced with permission from Phys. Rev. A , 1977, 15, 689)
interaction with a driving field and an incoherent interaction with a thermal

reservoir, i.e. spontaneous emission into the radiation field.440It was found that
only in the special case of the saturation limit is the principle of detailed balance
obeyed and that for this steady-state condition a generalized Boltzmann H theorem
may be derived for several definitions of generalized entropy. The experimental
conditions necessary to observe the intensity correlation function for the resonance
fluorescence of a single atom have been discussed.441Quantum electrodynamics
predict that the probability of observing a second photon from an atom that has just
emitted a photon tends towards zero as the time interval decreases, a property of
resonance fluorescencecalled anti-bunching that has yet to be observed experimen-
tally. Quantum-mechanical treatments of resonant light scattering have been
440 D. F. Walls, H. J. Carmichael, R. F. Gragg, and W. C. Schieve, Phys. Rev. A , 1978, 18, 1622.
"' H. J. Carmichael, P. Drummond, P. Meystre, and D. F. Walls, J . Phys. A: Math., Nucl. Gen.. 1978,11,
L121.
76 Photochemistry
reviewed.442The properties of resonance fluorescence from a two-level atom in
intense modulated laser fields have been investigated. The cases of phase
modulation,443 phase-frequency modulation,444 and intensity modulation 445
have all been considered. It has been shown that consideration of an intrinsic
linewidth for the driving laser field introduces an additional peak to the fluorescence
power spectrum of a weakly driven two-level atom.446
The statistical properties of three-level atom resonance fluorescence excited by
monochromatic laser radiation have been i n ~ e s t i g a t e d . An
~ ~ ’anti-bunching effect
is predicted, as are differences in the statistical properties of differently polarized
components of the fluorescence. An anisotropically polarized seven-line resonance
fluorescence spectrum has been predicted for a three-level atom having two closely
spaced excited and such a system is one of several treated in calculations
of atomic fluorescence radiance expressions for continuum excitation.449 The
Autler-Townes effect, which is a dynamic Stark splitting of energy levels in a strong
laser field, can be probed by using a second weak optical field to induce transitions
to a third level whose decay may be monitored separately. Numerical calculations
of such experiments have been made for the three-level sodium system 3’St F = 2,
32P,,2 F = 3, and 52S, F = 2 and show that at laser powers greater than that
equivalent to a Rabi frequency of 45 MHz the system behaves like an eight-level
system, i.e. hypefine structure cannot be ignored, a result that is consistent with
experiment.45 O
The effect of recoil is considered in a quantum-statistical theory of resonance
fluorescence valid for all orders of interaction with the laser field,451 and the
Doppler effect has been considered in a quantum-mechanical treatment of the
spectrum of resonance fluorescence from an atom in a perturber gas.452 The
resonance fluorescence from two interacting identical atoms or molecules has been
in~estigated,~’~ and the resonance fluorescence from molecules subject to inelastic
or reactive collisions has been treated theoretically in In the latter study
both classical and quantum-theoretical expressions for the intensity and polark-
ation of the fluorescence were derived for such collisions in which an antisotropic
distribution of rotational angular momentum is typically produced. The experi-
mental requirements to perform such studies are also discussed.
The results of recent detailed experimental work on resonance fluorescence from
two-level systems have been and as examples of recent experiments
442 B. R. Mollow in ‘Coherence and Quantum Optics’, ed. L. Mandel and E. Wolf, Plenum, New York,
1978, Vol. 4, p. 103.
443 P. Zoller and F. Ehlotzky, J . Phys. B. 1977, 10, 3023.
444 P. Zoller and F. Ehlolzky, Z . Phys. A , 1978, 285, 245.
445 P. Zoller, J . Phys. B, 1978, 11, 2825.
446 K. Wodkiewicz, Phys. Lett. A , 1978, 66, 369.
447 B. Sobolewska and R. Sobolewski, Opt. Commun., 1978, 26, 21 1 .
445
R . Kornblith and J. H . Eberly, J . Phys. B, 1978, 11, 1545.
449 G. D. Boutilier, M. B. Blackburn, J . M. Mermet, S. J. Weeks, H. Haraguchi, J. D. Winefordner, and N .
Omenetto, Appl. Opf.,1978, 17, 2291.
450 S. Swain and W. A. McClean in reference 442, p. 127.
45’ G. S. Agarwal and R. Saxena, Opt. Commun., 1978, 26, 202.
452 G. Neinhuis and F. Schuller, Physica B + C (Amsterdam), 1977, 92, 397.
453 C. Mavroyannis, Phys. Rev. A , 1978, 18, 185.
154 D. A. Case, G . M. McClelland, and D. R. Herschbach, Mol. Phys., 1978,35, 541.
455 (a) H. Walther in reference 4386, p. 129; (6) S. Ezekiel and F. Y. Wu in reference 4386, p. 145.
mention is made of the use of Haresonance fluorescence at 656.3 nm to monitor the
plasma conditions in a Tokamak reactor456 and of studies of the resonance
fluorescence of C1, 4 5 7 and Br2.458
Superjluorescence. Although superfluorescence is a property of an ensemble of
inverted atoms or molecules this is an appropriate point in the report to mention a
number of recent papers on this important topic. The general features of the
phenomenon of superradiance are as follows: if a system of atoms or molecules of
density n per unit volume is completely inverted at time t = 0 then the system emits
a short, intense, directional pulse (or pulses) of radiation whose peak intensity is
proportional to n2 at a time zD > 0, where the pulse delay time rD, is proportional
to n- I. This (Dicke) superradiant emission from an inverted population is called
superfluorescence (vide infra) and is to be distinguished from the emission
proportional to n2 that is given by atomic systems subjected to an intitiating
external pulse and referred to as swept-gain superradiance.
There is a considerable debate currently that concerns two different theoretical
approaches to superradiance, one being quantum-mechanical, the other semi-
classical. In the quantum-theoretical approach of Dicke collective energy eigen-
states of two-level atoms are defined and characterized by two quantum numbers,
M the energy quantum number and J the co-operation quantum number. For N
atoms then 0 < J < N / 2 and -J < M < J. Two extreme cases can be identified:
in the first case J z N / 2 and M = 0 and this is called a superradiant state, and in
the second case M = J = N / 2 and this fully excited state has become associated
with the term superfluorescence. The phenomenon may be regarded as collective
spontaneous emission. In the semi-classical approach the radiation field is treated
classically and the spontaneous emission arises from a noise term. Here the
phenomenon is a transient form of stimulated emission from a high-gain medium.
The latter theory has generally been more successful in accounting for experimental
observations. A number of interesting papers on the theory of superfluorescence
have been published (see references 442 and 459), including several on the
phenomenon of bistability in which systems of inverted atoms and molecules
exhibit phase transitions and which, for example, makes a Fabry-Perot filled with
such atoms behave as an optical transistor.
The close correspondence of the quantum and semi-classical theories has been
established in a recent investigation of the fluctuating properties of superradiant
and superfluorescent systems.460The early stages of a superfluorescent pulse have
been described, the pulse being initiated by zero point fluctuations of the atomic
polarization field.461A particular problem to be treated by theories of superradi-
ance is to account for the trains of ringing pulses observed in the superfluorescence
of HF which contrasts with the observation of single pulses from the carefully
4s6
V. S. Burakov, P. Ya. Misakov, P. A. Naumenkov, S. V. Nechaev, G. T. Razdobarin, V. V. Sernenov,
L. V. Sokolova, and I . P. Folomkin, Zh. Prikl. Spektrosk., 1978, 29, 1079.
457
D. Hwang and H. Chang, J . Mol. Spectrosc., 1978, 69, 1 1 .
4s8 H. Chang and D. Hwang, J . Mol. Spectrosc., 1977, 65, 430.
459 ‘Cooperative Effects in Matter and Radiation’, ed. C. M . Bowden, D. W. Howgate, H. R. Robl, and R.
Hermann, Plenum, New York, 1977.
460
A. Zardecki and R. Baribeau, Can. J . Phys., 1977, 55, 984.
461
R. Glauber and F. Haake, Phys. Letr. A , 1978,68, 29.
78 Photochemistry
studied Cs system. Oscillatory effects in superfluorescence have been investigated
by numerically solving both a generalized master equation 462 and a Markovian
master equation,463making it possible to compare the regions of applicability of
the two theories of superradiance. Oscillatory superfluorescence can be described
by the sine-Gordon equation,464and the presence of quantum beats and chirping in
superfluorescence has been discussed.465
There are several reports of experimental work on superfluorescencein references
442 and 459. The 7 P + 7 s transition in Cs at 3pm is ideally suited to studies of
superfluorescence, and this has made it possible to help meet stringent conditions
for the observation of ‘pure’ superfluorescence established theoretically for a
pencil-shaped volume of a pure two-level system.466Under ‘ideal’conditions in Cs
a single pulse was observed.467As the excitation density was increased multiple
pulses were observed which were probably separate pulses originating from
different parts of the sample. A requirement for the semi-classical and quantum
theories to be in agreement that has been established in recent theoretical work 463
is that the semi-classical tipping angle is equal to the square root of the number of
radiating particles. This result has recently been observed experimentally by
injecting a coherent pulse of known area into a completely inverted sample of Cs
atoms and measuring the delay of the output
A wave-front-reversal effect in which the superluminescence of a dye solution
acquires the original coherence of the exciting radiation has been observed,469and
the polarization properties of superluminescence in an anisotropically amplifying
medium have been in~estigated.~~’ The contributions of superluminescence and
stimulated emission to the emission properties of unstable photoisomers of
polymethine dyes have been studied, and this led to conclusions regarding the
influence of photoisomerization on the emission from these systems for different
excitation wavelengths.
Fluorescence. As in my last review only a very limited selection of the large number
of papers on the fluorescence properties of atoms and molecules are reported here.
More extensive coverage of this type can be found in later chapters.
Extensive reviews of the luminescence of inorganic compounds 4 7 2 and of
triboluminescence (mechanically produced electronic excitation as in the crushing
of crystals) 473 have been published. The wide application of laser-induced
fluorescencetechniques in studies of collision dynamics and of energy distributions
462
M. Gronchi, L. A. Lugiato, and P. Butera, Phys. Rev. A , 1978, 18, 689.
463 E. Ressayre and A. Tallet. Phys. Rev. A , 1978, 18, 2196.
464 J . A. Hermann, Phys. Lett. A , 1979, 69, 316.
465 R. Prakash and N. Chandra, Phys. Rev. Lett., 1979,42,443.
466 R. Bonifacio and L. A. Lugiato, Phys. Rev. A , 1975, 12, 587.
467 ( a )Q. H. F. Vrehen, H. M. J . Hikspoors, and H. M. Gibb in reference 442, p. 543; (b) H. M. Gibbs,
Q. H. F. Vrehen, and H. M . J. Hikspoors, Phys. Rev. Lett., 1977, 39, 547.
468 Q. H. F. Vrehen and M. F. H. Schuurmans, Phys. Rev. Lett., 1979,42, 224.
469 V. G . Koptev, A. M . Lazaruk, I . P. Petrovich, and A. S. Rubanov, Pis’ma Zh. Eksp. Teor. Fiz., 1978,
28,468.
“O
A. I. Odintsov, N. G. Turkin, and V. P. Yakunin, Pis’ma Zh. Tekh. Fiz., 1978, 4, 153.
471
A. M . Bonch-Bruevich, E. N. Kaliteevskaya, and T. K. Razumova, Kvantovuya Electron. (Moscow),
1978, 5 , 1113.
472 D. J . Robbins and A. J . Thompson, Electron. Struct. Magn. Znorg. Compd., 1977, 5, 153.
473
A . J . Walton, Adv. Phys., 1977, 26, 887.
in the fragments of photodissociation processes has been reviewed,474as has the use
of infrared fluorescence studies in vibrational spectroscopy.475There have been
interesting reports of fluorescence-based methods for the measurement of tempera-
tures in particle-laden combustion flows 476 and laser excited low-pressure
gases,477and the saturation of laser-induced fluorescence signals has been used to
measure the concentrations of CH and CN radicals,478and Na atom^,^" in flames.
A number of conclusions are reached in the latter study which restrict the use of
saturated atomic fluorescence intensities in the measurement of the total atomic-
number density in flames.
There are two important laser-based methods for determining homogeneous
linewidths, namely laser-induced fluorescence line-narrowing and hole-burning
(laser saturation of absorption). It is a relatively easy matter to achieve laser
linewidths significantly smaller than the homogeneous linewidth of the transitions
likely to be encountered in electronic spectroscopy, even at very low temperatures,
and such experiments using tunable lasers are finding increasing application.
Recent fluorescenceline-narrowing (FLN) studies of the spectroscopy of rare-earth
ions in glasses have, in the main, used non-resonant excitation which has a number
of important disadvantages. A recent paper has given details of a time-resolved
laser-induced FLN study of the 5D,+ 7F0fluorescence of Eu3+ in which a gated
vidicon detection system made it possible to use resonant excitation.480 The
homogeneous linewidth was found to be determined by the rate of phase-
interrupting, two-phonon Raman scattering processes. A theory of time-dependent
effects in FLN has been published which is based on coupled rate equations and
which is applicable when kTis much greater than the inhomogeneous l i n e ~ i d t h . ~ ~ ’
The FLN of a molecular gas in the resonator of a high-power single-mode laser has
been investigated t h e ~ r e t i c a l l yand
, ~ ~an
~ interesting study of FLN in ruby crystals
has been
The close relation between FLN and hole-burning, particularly as regards the
spectral shapes of the two effects, has been The holes are produced by
the disappearance of resonantly excited molecules and, as in FLN, if the laser
linewidth is sufficiently narrow the width of the hole is related to the homogeneous
linewidth of the transition. The envelope of such a transition can usually be
approximated by a Lorentzian curve. The disappearance can be the result of
photochemical or photophysical processes, for example hole-burning techniques
have been used recently in studies of the reversible photochromism of hydroxy-
quinones arising from both intra- and inter-molecular hydrogen bonds 4 8 5 and of
4’4 J . L. Kinsey, Annu. Rev. Phys. Chem., 1977, 28, 349.
475 G . C. Pimentel in ‘Vibrational Spectroscopy- Modern Trends’, ed. A. J . Barnes and W. J. Orville-
Thomas, Elsevier, Amsterdam, Netherlands, 1977, p. 33.
476 R. M. Kowalik and C. H. Kruger, Combust. Flame, 1979, 34, 135.
477 L. I. Kleinman, R. E. Weston, jun., and G. W. Flynn, J . Appl. Phys., 1978, 49, 4328.
478 P. A. Bonczyk and J. A. Shirley, Combust. Flame, 1979, 34, 253.
479 R. A. Van Calcar, M. J. M. Van de Ven, B. K . Van Uitert, K . J. Biewenga, T. Hollander, and C. T. J.
Alkemade, J . Quant. Spectrosc. Radiat. Transfer, 1979, 21, 1 1 .
480 M. A. El-Sayed, A. Campion, and P. Avouris, J . Mol. Struct., 1978, 46, 355.
481 D. L. Huber, D. S. Hamilton, and B. Barnett, Phys. Rev. B, 1977, 16, 4642.
E. Doepel and D. Kuehlke, Czech. J . Phys., 1978, B28, 141.
*” P. M. Selzcr, D. L. Huber, B. B. Barnett, and W. M. Yen, Phys. Rev. B, 1978, 17, 4979.
484 J. M. Hayes and G . J. Small, Chem. Phys., 1978, 27, 151.
48s F. Graf, H.-K. Hong, A. Nazzal, and D. Haarer, Chem. Phys. Lert., 1978, 59, 217.
80 Photochemistry
aromatic hydrocarbons in low-temperature glasses where there is an excited-state
mediated interconversion of molecules between sites in an asymmetric double-well
An interesting paper has established that sub-nanosecond fluores-
cence lifetimes can be measured using the hole-burning method.487The homoge-
neous linewidth of the zero phonon, electronic origin of the 1B3u+ 'Alg, S , + So
transition of s-tetrazine in benzene crystals at low temperature ( < 1.5 K), was
determined from the measured hole-width of 0.7 f 0.1 GHz to be 350 & 50 MHz.
This corresponds to a fluorescent lifetime of 455 - 5 5 7 5 ps, in excellent agreement
+
with the figure of 450 f 55 ps obtained using picosecond pulsed-laser techniques.

Marked differences were observed between the inhomogeneous widths of the purely
electronic and the l6aO2 vibronic transition. A remarkable variation in the
homogeneous linewidths of the electronic origin and fourteen single vibronic levels
in the S , e So transition of free-base porphin(H,P) in an n-octane crystal at 4.2 K
has been The homogeneous linewidths were found to vary from 4 GHz
to 180GHz, and the results are summarized in Figure 22. No correlation was found
Homogeneous I inewidth Ir,)of A p i b r o n i c lines

Figure 22 Upper part: schematic excitation spectrum of A, vibronic lines relative to the origin
'.
at 16 331 cm- Lower part: homogeneous width of the same lines from hole-burning
measurements
(Reproduced with permission from Chem. Phys. Lett., 1979, 61,421)
between the linewidth and either the excess vibrational energy or the symmetry
species of the vibration. The intriguing question is whether the observed variation
arises from an intramolecular effect, a characteristic of the porphin, or from the
coupling of the guest to the host lattice.
486 J. M. Hayes and G. J . Small, Chem. Phys. Lett., 1978, 54, 435.
487 H. De Vries and D. A. Wiersma, Chem. Phys. Lett., 1977, 51, 565.
488 S. Voelker and R. M. Macfarlane, Chem. Phys. Lett., 1979, 61, 421.
A remarkably detailed study of the B'llu-X'Z,+ band system of Na, has been
published.489 The use of laser-induced fluorescence techniques and a 9.3 m
spectrograph led to the observation of over 25 000 lines with absolute frequencies
measured to better than 0.010cm- '. The coefficients in the Dunham expansion of
v(u',u",S,s') in a region of the potential where it is believed to converge
satisfactorily were determined sufficiently accurately to begble to reproduce 12 591
lines in the spectrum with an r.m.s. deviation between observed and calculated
frequencies of 0.01 1 cm- I . The dissociation energies of the X and B states were
found to be 5988 and 3116cm-', respectively. An upper limit of
6.3 O.Skcalmol-' for the CH, (i?'Al-T3Bl) energy separation has been
obtained from a study of the laser-induced fluorescence of the CH, (i?'Al)radical
produced by the nitrogen laser photolysis of ketene CH,C0.490This is a somewhat
lower value than has been obtained by recent ab initio calculations (see Section 2).
Large variations in the fluorescence lifetimes of individual rotational levels in the
(0,O) band of the lowest allowed transition in CO ( A 'n-X'Z+) have been observed
in a study which uses tunable vacuum ultraviolet radiation generated by four-wave
frequency mixing in Mg v a p o ~ r . The ~ ~ 'variations arise from perturbations of the
All7 levels by e3E- and d3Ai states. Resonance fluorescence from a single
rovibronic level of the A ' A , state of formaldehyde excited with 337.5 nm radiation
from a krypton laser was found to comprise vibrational progressions in the ground-
state vibrations v," (carbonyl stretching), v3" (in-plane bending), and even quanta
of vqR (out-of-plane bending), all of which have the_samesymmetry as the level from
which the excitation took place.492Details of the A 2 A l - f 2 B 1emission spectrum of
a NH, radical have been analysed to give the molecular constants of the (010) level
of the f 2 B l ground state,493and the observation of A N = + 2 transitions in the
fluorescence from the A 2 B , state of NO, is evidence of a spin-orbit coupling
effect.494A very large hyperfine splitting, in excess of the Doppler width of the O,,
(O,O,O) 2 level of the PH, radical, has been observed which arises from the Fermi
interaction of 1P,495 and variations in the fluorescence lifetime following pulsed
dye laser excitation of different vibrational levels in the state of this radical have
been reported.496A study of the fluorescence decay of laser excited SO, has shown
that the states responsible for the lpng-lived and short-lived emission components
do not decay independently and support their assignment to the ' B , and ' A , states,
respe~tively.~~' A study of SO, fluorescence and SO,-sensitized biacetyl phos-
phorescence at higher pressures where the short-lived fluorescence component is
strongly quenched have shown that there is a common precursor to both the ' B ,
state and the phosphorescent 3B1state, the latter probably being populated via a
489 P. Kusch and M . M. Hessel, J . Chem. Phys., 1978, 68, 2591.

490 J. Danon, S. V. Filseth, D . Feldrnann, H. Zacharias, C. H. Dugan, and K. H. Welge, Chem. Phys.,
1978, 29, 345.
49' A. C. Provorov, B. P. Stoicheff, and S. Wallace, J . Chem. Phys., 1977, 67, 5393.
492 J . L. Hardwick and S. M . Till, J . Chem. Phys., 1979, 70, 2240.
493 M. Vervloet, M. F. Merienne-Lafore, and D . A. Rarnsey, Chem. Phys. Lett.. 1978, 57, 5 .
494 J. C. D. Brand and P. H. Chiu, J . Mol. Spectrosc., 1979, 75, 1 .
495 R. F. Curl, Y. Endo, M. Kakimoto, S. Saito, and E. Hirota, Chem. Phys. Lett., 1978, 53, 536.
496 R . E. Huie, N . J. T. Long, and B. A. Thrush, J . Chem. SOC.,Furaduy Trans. 2, 1978, 74, 1253.
497 F. Su, J. W. Bottenheim, H. W.Sidebottom, J. G. Calvert, and E. K. Damon, fnt. J . Chem. Kinet.,
1978, 10, 125.
82 Photochemistry
Renner-Teller coupling mechanism.498 Non-exponential fluorescence decays of
thiophosgene vapour observed following excitation into single vibronic levels of the
S , manifold under isolated molecule conditions have been interpreted as evidence
for reversible radiationless transitions involving low-lying triplet states.499Some
important reassignments have been made for prominent emission bands of I, and
Br, following the vibrational analysis of isotope spectra. '0° The strong lasing
transitions of I, and Br, at 340 and 290 nm, respectively, were previously assigned
to E -+ B transitions, but this is incorrect and the proper assignment is
'.
1432, 2g3n + 2431, 2u3n,D' + A (The four-digit prefixes relate to Mulliken's
notation for the molecular orbitals involved.)501A number of recent investigations
have observed pronounced non-linear Stern-Volmer plots for the self-quenchingof
gaseous UF, fluorescence following excitation in the A-X band. A simple kinetic
scheme based on two collisionallycoupled fluorescent excited states, A and A,, has
been shown to account for the available quenching data.,', A strong temperature
dependence for the self-quenching rate constant may indicate that the quenching
mechanism is a collision-induced dissociation to UF, and F.,03
A consistent picture of the fluorescence properties of aqueous solutions of
tryptophan and other substituted indoles may finally emerge following the recent
observation of two components in the fluorescence spectrum of tryptophan with
emission maxima of 350 and 335 nm and mean lifetimes of 3.14 and 0.51 ns,
respectively.504There is some discussion on the origin of the two bands, the most
likely being that they arise from two different conformers which do not interconvert
on the time-scale of the fluorescence and which have different radiationless decay
rates due to their different indole ring-sidechain interactions.
A series of papers on the effects of high pressure (up to 140kbar) on the
photophysical properties of molecules have supported the idea that the energy
levels of excited states relative to the ground state, and to each other, can be
continuously varied by changing external pressure. A configuration co-ordinate
treatment of optical transitions in condensed phase systems has been developed,
and expressions for the changes in the peak position and half-width of absorption
and emission bands have been obtained in terms of three parameters: the ratio of
the excited- and ground-state frequencies (almost constant with changes in
pressure), a dimensionless coupling coefficient, and a co-ordinate displacement, A,
of the excited state relative to the ground state. The modes that are most strongly
coupled to the pressure are intermolecular. In general the large bulk volume
changes that are observed for typical systems on increasing the pressure are not
reflected in the only relatively small changes in intramolecular properties, e.g.
intramolecular frequencies typically change by only 1 or 2% for a 100kbar change
in the pressure. An interesting manifestation of the mainly intermolecular origin of
4yu
F. Ahmed, K. F. Langley, and J . P. Simons, J . Chem. SOC.,Faraday Trans. 2, 1977, 73, 1659.
499 D . Phillips and R. P. Steer, J. Chem. Phys., 1977, 67, 4780.
J . Tellinghisen, Chem. Phys. Lett., 1977, 49, 485.
501
R. S. Mulliken, J . Chem. Phys., 1971, 55, 288.
502 R. C. Oldenborg, W. W. Rice, and F. B. Wampler, J . Chem. Phys., 1978, 69, 2181.
503
A. Andreoni, R. Cubeddu, S. De Silvestri, and F. Zaraga, Chem. Phys. Lett., 1977, 48, 431.
504 D.M. Rayner and A. G. Szabo, Can. J . Chem., 1978, 56, 743.
'05 ( a ) D. J. Mitchell, G . B. Schuster, and H. G. Drickamer, J . Chem. Phys., 1977, 67, 4832; (b) D. J.
Mitchell, H. G. Drickamer, and G. B. Schuster, J . Am. Chem. Soc., 1977, 99,7489.
506 H. G. Drickamer, C. W. Frank, and C. P. Slichter, Proc. Natl. Acad. Sci. USA, 1972, 69, 933.
the observed effects is the appearance of excimer emission at high pressures as is
illustrated in a recent study of pyrazine and some of its methylated derivatives.”’
Changing the pressure is a convenient way to bring about isothermal changes in
viscosity, and this effect has been used in a study of the viscosity dependence of the
fluorescence efficiency of Crystal Violet and Auramine 0,in which pressures up to
11 kbar on solutions of methanol, isopropanol, isobutanol, and glycerol gave a
continuous viscosity change from lo-, to lo3 poise at room ternperat~re.”~ The
results confirmed an q2/3 dependence of fluorescence intensity observed previously
in non-rigid aromatic molecules. The effect has also been used in studies of the
viscosity dependence of fluorescence-quenching rate constants ’09 and of the
deactivation via twisting of the planar excited singlet state of trans-~tilbene.~”A
theoretical approach related to the configuration co-ordinate model has been used
to interpret the pressure and temperature dependence of the fluorescence of 9-
methyl- and 9, IO-dibr~mo-anthracene.~~ The concept of activation volume based
on the Eyring transition-state theory was used to correlate the data.
The fluorescenceexcitation spectrum of the 60’ band of the B,, t ‘ A , transition
of benzene rotationally cooled at 0.3 K using either a pulsed. or a continuously
operated supersonic-free jet showed a band contour that was in almost perfect
agreement with the model of Callomon et al. (see reference 182).’12 A very
interesting paper on the fluorescence lifetimes and quantum yields of benzene,
toluene, [‘H,]aniline, and [’H,]aniline vapours excited into the higher vibronic
levels of their S , states has shown that the previously well characterized but
unexplained ‘third channel’ of deactivation in benzene is common to all the
molecules.513The highly specific form of the ‘third channel’ in benzene is replaced
in more complex molecules by an exponential increase of non-radiative decay rate
with excitation frequency when a certain critical value for the excitation energy has
been exceeded. In intermediate-size molecules the anharmonic coupling between
‘active’ and ‘inactive’ modes is responsible for the non-selective excitation. The
results show that the ‘third channel’ has some of the characteristics associated with
an internal conversion process. The fluorescence of anthracene in a 2-methyl-
tetrahydrofuran glass at liquid-helium temperatures showed a remarkable series
of changes between sharp and diffuse character as the excitation energy was
increased from 0 to 2000cm-’ excess energy,514and the elusive fluorescence of
pyridine has finally been observed. ’
An earlier observation of two components in the fluorescence decay of trans-
’
stilbene was not confirmed in a recent study using pure samples.’ The long-lived
component which had been attributed to a return to a trans geometry after initial
photoisomerization could be induced by use of impure samples. The new results
show that the photoisomerization step in which the trans excited state converts to a
507 D. J. Mitchell, G. B. Schuster, and H. G. Drickamer, J . Chem. Phys.. 1979, 70, 2443.
”* L. A. Brey, G. B. Schuster, and H. G. Drickamer, J . Chem. Phys., 1977, 67, 2648.
509 L. A. Brey, G. B. Schuster, and H. G. Drickamer, J . Chem. Phys., 1977, 67, 5763.
510 L. A . Brey, G. B. Schuster, and H. G. Drickamer, J . Am. Chem. Soc., 1979, 101, 129.
’’I B. Hammerich, R. Schmidt, and H.D. Bauer, Ber Bunsenges Phys. Chem., 1979, 83, 198.
512 S. M. Beck, M. G. Liverman, D. L. Monts, and R. E. Smalley, J . Chem. Phys., 1979, 70, 232.
513 M. Jacon, C. Lardeux, R. Lopez-Delgado, and A. Tramer, Chem. Phys., 1977, 24, 145.
514 J. Friedrich, G. Flatscher, and F. Doerr, Ber. Bunsenges. Phys. Chem., 1978, 82, 392.
515 I. Yamazaki and H. Baba, J . Chem. Phys., 1977, 66, 5826.
516 F. Hiesl, J. A. Miehe, and B. Sipp., Chem. Phys. Lett., 1979, 61, 115.
84 Photochemistry
twisted excited state has an Arrhenius temperature dependence with an E, of
2.6 kcal mol- I . An investigation of the fluorescence properties of two constrained
conjugated trienes has provided clear information about the photophysical
properties of polyenes free from uncertainties regarding the contribution to these
properties from conformation fle~ibility.~ l 7 The two molecules were cholesta-
4,6,8( 14)-triene (4) and cholesta-5,7,9( 1l)-triene-3/?-OH (5). In (4) the lowest-
(4)
energy transition was found to be the weak forbidden transition 'Ag* +- 'A,, but in
(5) the excited-state ordering was changed and the lowest-energy transition is the
strongly allowed 'B,* +- lA,. This valuable study shows clearly that geometry can
determine the order of the excited states. Studies of the temperature dependence of
the fluorescence properties of all-trans-diphenylhexatrieneand octatetraene have
provided firm evidence for the S,( 'A,*) and S2('B,*) state assignments proposed
earlier to explain the anomalous photophysical behaviour of these molecules. ''
Anti-Kasha and Anti-Stokes Fluorescence. A number of new research areas have
been explored in a notable series of papers on the low quantum yield (& < 10- 3),
very short-lived (zF < s) emission from the higher excited singlet states of a
number of complex molecules, principally aromatic hydrocarbons. The studies
were initiated by the observation of ultraviolet fluorescence from solutions of the
xanthene dyes Rhodamine 6G and B, following excitation by consecutive two-
photon absorption, a process which when using relatively low-power long-duration
laser-pulse excitation has the important advantage of avoiding the excitation of
impurity fluorescence.5 1 The excitation process is illustrated in Figure 23 where
the first photon, Ao, populates S, and the second photon, Al or A2, populates higher
singlet states by one-photon allowed transitions from S,. This is followed by
S, + So fluorescence emission. As well as establishing that emission did arise from
several excited states above S, these initial studies on the xanthene dyes and rubrene
showed the presence of very strong polarization effects, as expected from short-
lived excited states. In addition it was found that the high frequency limit of the
fluorescence was dependent on the excitation wavelength, an indication that
emission occurred from unrelaxed vibrational levels. The studies were extended to a
number of fluid solutions of polycyclic aromatic hydrocarbons, using the same
technique in which the two photons were of the same frequency, originating from
the same laser, and a series of broad, essentially featureless emission spectra were
observed. 5 2 0 The most remarkable observations were made, however, using a
modified technique in which each photon was obtained from an independently
51' J. R. Andrews and B. S. Hudson, Chem. Phys. Lett., 1979,60, 380.
5'8 J. B. Birks, G. N. R. Tripathi, and M. D. Lumb, Chem. Phys., 1978, 33, 185.
519 H. B. Lin and M. R. Topp, Chem. Phys. Lett., 1977, 47, 442.
520 H. B. Lin and M.R. Topp, Chem. Phys. Lett., 1978,48, 251.
tunable laser. A study of 3,4,9,10-dibenzpyrene (S, t So 3 430nm) revealed a
strong dependence of the vibrational structure of the fluorescence spectrum on the
energy of the second photon which is illustrated in Figure 24. A progression
I I I m
lnhomogeneout
width
Figure 23 Energy diagram illustrating the dependence of the Sn,l + So Juorescence

bandwidth on the excitation wavelength. I, 11, and I11 represent three sample sites having
direrent energies within S , but which are not resolvable within the envelope of thejrst principal
vibrational band of s,. Following A0 excitation, relaxation occurs to efectively a single S , level.
Secondary excitation reaches diyerent low-energy vibrational levels of the sites I, 11, and 111in
the lowest principal vibrational band of S,. I , excitation gives a broadJluorescence band,
whereas I , excitation gives a narrow bandwidth
(1460 f 60cm-') was observed in each of the spectra with an origin at the
combined photon energy and a marked trend towards a narrower bandwidth at
lower excitation energies. An additional feature was the appearance of fixed-
position emission bands for excitation R > 590. A subsequent study of 3,4-
benzpyrene showed more clearly the broadening of members of the progression,
whose origin is at the effective excitation energy, towards lower energy.52' The
general picture emerging from these studies is that a process of site selection is
taking place, as illustrated in Figure 23, which is related to the experiments on
fluorescence line-narrowing and hole-burning mentioned in an earlier section. The
very short lifetime of the fluorescence (the measured bandwidth of highest-
'
frequency band of x 300cm- gives a lower limit to the lifetime of 0.02 ps) means
that it is a unique probe of homogeneous linewidths in fluid solutions, it being faster
than the rate of molecular site exchange. The broadening observed in the
progression reflects the competition of fluorescence emission with vibrational
redistribution and internal conversion. Other features of the experiments including
the measurement of the quantum yields of this very weak fluorescence and the
shapes of the Franck-Condon envelopes of the vibrational progressions have been
52'
K . J. Choi, L. A. Halliday, H. B. Lin, and M. R . Topp in 'Picosecond Phenomena', ed. C. V. Shank,
E. P. Ippen, and S. L. Shapiro, Springer-Verlag, Berlin, 1978, p. 27.
86 Photochemistry
discussed,522and the use of the consecutive two-photon absorption technique to
measure the singlet-state lifetimes of weakly fluorescent molecules such as acridine
in non-polar solutions has been described. 5 2 3
50
I \I \ 550
I \ I\ 580
"/
50
/ \ j- 610
x/n m
Figure 24 Montage of high-frequencyfluorescence spectra obtained by two-laser excitation of
3,4,9,1@dibenzpyrenein hexane at 300 K . Intensities correctedfor the absorption of a single 7-54
filter. Spectra useful down to about 235 nm. Secondary excitation wavelengths are noted on the
spectra: the arrows denote the position of Jeff
A vibrational analysis of the S, + S , fluorescence of azulene in a naphthalene

mixed crystal at 4.2 K has been No explanation for the weakness of
this spin and symmetry allowed ' A , + ' 4 ,which seems to be intrinsic to the
azulene structure, has yet been found. The often cited 'anomalous' S, + So
emission is in fact 'normal' with respect to theoretical estimates of its rate. A
summary of the photophyskal parameters of the lowest excited singlet states of
'*' K . J. Choi, L. Halliday, H. B. Lin, and M. Topp in reference 160, p. 155.
523
L. Halliday, H. B. Lin, and M. Topp in reference 521, p. 314.
524 G. D. Gillespie and E. C. Lim, J . Chern. phys.. 1978, 68, 4578.
azulene is presented in the paper. An emission previously assigned to T , --* So
phosphorescence was shown to be a combination band of S,-S, fluorescence. An
S , --* So emission has been observed from the C-nitroso compound p-
dimethylaminonitrosobenzene, which has a broad transparent region between its
first (red) and second (violet) absorption bands.525No such emission was found in
N-nitrosoamino compounds such as N-nitrosodiphenylamine. S , emission has
been observed from chrysen and 3,4-benzophenanthrene in the vapour phase under
collision-free conditions.526 As in the case of other hydrocarbons studied
previously, e.g. pyrene, the S , fluorescence-decay time exceeds the pure radiative
lifetime calculated from the So + S , absorption spectrum, and they are also
examples of intermediate strong coupling between a single S , vibronic level with a
number of levels of the S , manifold. Luminescence from upper excited levels of 1,2-
benzanthracene in heptane has been ~bserved,’~’ and an interesting discussion of
the photophysical properties of the molecule azuleno[5,6,7-cd]phenalenehas been
published.528In the latter molecule the S3,SZ energy separation is small, resulting in
a slow S , + S , IC process and the observation of S , + So fluorescence.
A treatment of anti-Stokes luminescence by quantum statistics considers both
co-operative and sequential sensitization mechanisms.5 2 9 The hot luminescence of
Rhodamine 6G in ethanol and glycerin has been found to be strongly polarized,530
and the temperature dependence of the relative quantum yield for anti-Stokes and
Stokes excited fluorescence of water-glycerol solutions of Rhodamine 6G was
found to be quite strong.531
Fluorescence Quantum Yields. The measurement of the absolute quantum yield, &,
of the oxazine dye Cresyl Violet, using both photomicrocalorimetry and the newer
laser technique of thermal blooming, has established a useful new standard for the
red region of the spectrum.532A value of $F = 0.54, was established for an air-
equilibrated dilute methanol solution at 22 “C for excitation from 540 to 640nm.
Up to the time of this study there were only two primary standards, quinine
bisulphate ($F = 0.56) and disodium fluorescein ($F = 0.93), measurements
against which give relative quantum yields using standard methods, and neither of
them can be used in the red region. The introduction of the thermal-blooming
technique, mentioned in my previous report, to the measurement of absolute
luminescence quantum yields is an important development. Strong arguments have
been advanced for the adoption of this simple and versatile technique for such
mea~urernents.~’~ The method has already been used to give a value for the
absolute 4Fof sodium fluorescein in 0. IN aqueous sodium hydroxide at concen-
trations <10-5m01dm-3 of 0.95 f 0.03, a result that is independent of any
previous determination.553A new photoacoustic spectroscopic (PAS) method for
525 N. J . Bunce, Chem. Phys. Lett., 1978, 59, 66.

52h J. Langelaar, M. W. Leewo, J. D. W. Van Voorst, and R. P. H. Rettschnick, Chem. Phys. Lett., 1979,
62, 14.
521 V. L. Bogdanov and V. P. Klochkov, Opt. Spektrosk., 1978,45, 95.
528 A. R. Holzwarth, K . R. Nagir, and U. P. Wild, Chem. Phys. Lett., 1977, 46, 473.
529 P. F. Gonzalez-Diaz, Opt. Commun., 1978, 26, 437.
530 V. L. Bogdanov, V. P. Klochkov, and B. S. Neporent, Opt. Spektrosk., 1977, 43, 1184.
53’ C. Bojarski, A. Biyko, R. Biyko, and R. Twardowski, Acta Phys. Pol. A , 1978, 54, 713.
532 D. Magde, J . H . Brannon, T. L. Cremers, and J. Olmsted, tert., J . Phys. Chem., 1979, 83, 696.
533 J. H. Brannon and D. Magde, J . Phys. Chem., 1978, 82, 705.
88 Photochemistry
the measurement of the absolute 4Fvalues of dye solutions has been described.534
From the measurement of the PAS signal intensities following excitation into both
the S , and the S , energy levels of the dye, a value for 4,can be simply obtained. The
method avoids the use of a non-fluorescent standard and relies only on the
assumption that the S, + S , IC process has unit efficiency. The origins of the wide
variation in the published $F values for 9,1O-diphenylanthracene,frequently
suggested as a 4Fstandard, have been investigated using a modified calorimetric
procedure which is suitable for optically dilute samples.535The careful study
established that qbF was significantly solvent-dependent but that it showed no
excitation wavelength dependence. A technique for the measurement of the 4Fof
ions in solids, e.g. Nd3+ in ED2 glass, has been described; it involves the
measurement of the photoacoustic signal and fluorescent lifetime as a function of
the ions c ~ n c e n t r a t i o n . ~ ~ ~
The proceedings of a workshop on standardization in spectrophotometry and
luminescence measurements contain several papers on quantum-yield measure-
ments. 5 3 7 The effects of self-quenching and of excitation-energy transfer on
photoluminescence quantum-yield measurements have been discussed theoreti-
ally.^^^ The model used considered the formation of dimers and the dipoldipole
mechanism of energy transfer. The formula for calculating luminescence quantum
yields from measurements of fluorescence intensity relative to that of a standard
substance should be modified to take account of polarization effects in the
instrumentation and of the residual emission anisotropy of the fluorescent
sample.539A correction factor to account for these effects is probably significant for
highly viscous systems. It has been suggested that atomic fluorescence quantum
yields can be measured by observing the delay in the emission of stimulated
radiation from a chemical laser following the initial photodissociation step. 540 The
addition of a fluorescence quencher to a fluorescent system in solution can either
increase or decrease the temperature dependence of the fluorescencequantum yield.
This arises because of the different temperature dependence of the two principle
contributory factors; non-radiative processes within the fluorophore and the
diffusion of the quencher and fluorophore in the liquid. This effect has been
investigated for indole and phenol in water and dioxan and found to give a
consistent picture of the effects and its origins.54'
Fluorescence Polarization. A theory of the emission analogue of magnetic linear
dichroism called magnetic linearly polarized emission (MLPE) has been developed
for the case of molecules which are paramagnetic in either their ground or first
excited states and which are isotropically distributed in a rigid matrix.542MLPE, in
which emission is analysed for its linear polarization parallel and perpendicular to
an applied magnetic field, may arise from Zeeman splittings in either the ground or
534 M. G. Rockley and K. M. Waugh, Chem. Phys. Lett., 1978, 54, 597.
535 M. Mardelli and J. Olmsted, tert., J. Photochem., 1977, 7 , 277.
536 R. S. Quimby and W. M. Yen, Opt. Lett., 1978, 3, 181.
537 Natl. Bur. Stand., Spec. Publ., No. 466, 1977.
538 C. Bojarski, Acta Phys. Chem., 1977, 23, 11.
539 J. A. Poole and A. Findeisen, J. Chem. Phys., 1977, 67, 5338.
540 N. Kh. Petrov, N. F. Chebotarev, and S. Ya. Pshezhetskii, Kvantovaya Elektron. (Moscow), 1977,4,
2248.
541 G. Laustriat and D. Gerard, J. Phys. Chem., 1978, 82, 746.
54Z J. P. Riehl and F. S . Richardson, J . Chem. Phys., 1978, 68, 4266.
emitting states, from field-induced mixing of molecular wavefunctions, and from
field-induced molecular orientation (field-induced orientation of supramolecular
assemblies is a recognized technique in biophysical investigations). The paper
considers only the first of these mechanisms but nevertheless was able to
-+
demonstrate theoretically significant differences in MLPE spectra arising from
photoselection effects, shown in Figure 25 for a C+ t n transition in linear
OAbsorption
e-7
7 Absorption
,,A?.
r A b sorption
CJ-Absorption
3 -2.5 0 2.5 f
Encrgy/c m - '
Figure 25 Calculated MLPE (AI) and total emission ( I )spectra for the Zg+c ll, transition
with c-polarized molecular absorption and n-polarized molecular absorption. u = 0",
/3 = O", T = 4.2K, B = 2.5T, and A = l.Ocm-'
(Reproduced with ptrmission from J . Chem. Phys., 1978, 68, 4266)
molecules, which should be of value in investigations of electronic structure in

luminescent molecular systems. Variations of the degree of polarization of
fluorescence within the fluorescence spectrum itself have been predicted in a
theoretical study of collisional depolarization effects.543
There have been a number of theoretical treatments of fluorescence polarization
in non-crystalline oriented media published recently, reflecting the widespread
application of this technique, particularly in the biological sciences. A method for
the three-dimensional structural analysis of uniaxial oriented media, which uses a
combination of polarized absorption and emission experiments, has been de-
scribed,544and a theory of the fluorescencepolarization decay of a fluorophore in a
restricted environment, which should find wide application, characterizes the
process in terms of two parameters, a 'wobbling' diffusion constant and a degree of
orientational constraint. 5 4 5 Theories of fluorescence polarization in uniaxial liquid
543
W. Ekhmenburg and F. Schuller, Z . Naturforsch., Ted A , 1977, 32, 558.
544 L. Marguiles and A. Yogev, Chem. Phys., 1978, 27, 89.
545
K . Kinosita, jun., S. Kawata, and A. Ikegami, Biophys. J., 1977, 20, 289.
90 Photochemistry
crystals,546in uniaxial polymers,547and in magnetically oriented photosynthetic
systems548 have appeared. A detailed model of the torsional dynamics and
resultant fluorescence depolarization of linear molecules has been developed. 549
The model considers N +
1 identical rods connected at their ends by torsion
springs and undergoing rotational Brownian motion about their fixed symmetry
axes. Four zones in the fluorescence anisotropy decay are identified with certain
types of motion of the chain. The model is applied to results obtained for ethidium
bound to DNA, as is another model which considers the macromolecule as a
semiflexiblechain.’” The second model suggests that twisting motions of the chain
are mainly responsible for the observed depolarization. A related theoretical
treatment of Acridine Orange bound to DNA has also been p ~ b l i s h e d . ~ ”
A theory of self-depolarization and luminescence decay has been developed in
terms of a model in which the excited molecule is at the centre of an active shell
whose inner radius is the point at which the Foerster interaction is the largest
contributor to the energy migration and whose outer radius is set by the reach of the
Foerster interaction. 5 2 Good agreement was found between the critical distance
values, Ro, obtained using the model and obtained from spectral measurements.
Expressions for the concentration dependence of the time-dependent emission
anisotropy have been obtained for the and the anistropy decay for the
particular case of a mean acceptor concentration of one molecule inside a sphere of
radius R, and for t < z, where z is the fluorescence lifetime, was shown to differ
from the Foerster theory expression [exp(-aJt/z)] by a factor of 0.61 in the
exponent.554 A new expression for concentration depolarization has been ob-
tained,’” and a numerical comparison of various theoretical expressions for this
effect found that a Monte-Carlo method in which the excitation migration was
explicitly included gave the best results (see Section 5).556 Errors introduced by
using approximations to the e - term in the concentration-versus-fluorescence
expressions have been discussed. ’
Non-linear effects in the concentration
depolarization of fluorescencehave been investigated theoretically and experiment-
ally.558In the study, solid solutions of Rhodamine B, Primulin, and Acridine
Yellow in poly(viny1 alcohol) were exposed to laser radiation. The concentration
depolarization in mixed fluorescent dye solutions has been in~estigated,~ 5 9 and
such an effect in glycerol-water solutions of mercuruchrome has been attributed to
the formation of dye aggregates.
546 L. L. Chapoy and D. B. Dupre, J. Chem. Phys., 1978,69, 519.

547 J. P. Jarry and L. Monnerie, J. Polyrn. Sci., Pol-vrn. Phys. Ed., 1978, 16, 443.
548 R. S. Knox and M. A. Davidovich, Biophys. J., 1978, 24, 689.
549 S. A. Allison and J. M. Schur, Chem. Phys.. 1979, 41, 35.
550 M. D. Barkley and B. H. Zimm, J. Chem. Phys., 1979, 70, 2991.
55’ G. P. Kishchenko and A. D. Gruzdev, BioJzika, 1978, 23, 801.
552 A. Kawski and K. Nowaczyk, Acta Phys. Pol. A , 1978, 54, 777.
553
J. Kaminski and A. Kawski, Z . Naturjorsch., Tei/ A , 1977, 32, 1339.
554 J. Kaminski, A. Schmillen, and A. Kawski, Z . Naturjorsch., Teif A , 1978, 33, 1001.
555 E. N. Bodunov, Zh. Prikl. Spektrosc., 1977, 26, 1123.
556 E. N . Bodunov, Izv. Akad. Nauk SSSR, Ser. Fiz., 1978, 42, 303.
557 R. B. Lam and J. J. Leary, Appl. Spectrosc., 1979, 33, 17.
”* E. S. Voropai, V. A. Gaisenok, I. A. Dudarev, I. N. Kolev, and A. M. Sarzhevskii, Zh. Prikl.
Spektrosk., 1977, 26, 678.
559 R . K. Bauer and H. Cherek, Acta Phys. Pol. A , 1977, 52, 875.
560 M. L. Pandya and M. K . Machwe, J. Lurnin.. 1979, 20, 51.
A new red-edge effecthas been reported in which a number of molecules, 1- and 2-
naphthylamine and various derivatives, anthracene, and indole in propylene glycol
solutions, exhibit a lowering in their emission anisotropy at the red edge.561This
increase in the rotation rate, which approaches that expected for out-of-plane
rotation, is attributed to the existence of a red-edge transition moment, in
absorption and emission, normal to the plane of the aromatic rings which could
arise from the coupling between out-of-plane nuclear vibrations and an in-plane
transition moment. It is also suggested that red-edge excitation excites preferen-
tially a group of solvent-fluorophor complexes with the least-stable electronic
states, perhaps those stabilized by the weaker out-of-plane polarizabilities of
aromatic molecules. A shift in the fluorescence emission maximum of an acidic
solution of quinine sulphate on excitation into the red edge of the absorption
spectrum, which was found to depend on viscosity, temperature, deuteriation of the
solvent, and solute concentration, has been interpreted in terms of excited-state
proton transfer. 562 An interesting paper has suggested that a number of red-edge
anomalies can be attributed to the heterogeneous broadening of electron-
vibrational levels on energy transfer.563A quantitiative test of this idea on the red-
edge shift in the fluorescence maximum and increase in the emission anisotropy
observed for 4-aminophthalimide in poly(viny1 alcohol) films was successful.564
A fluorescence polarization study of solid films of all-trans, 9-cis, and 13-cis
retinals found no evidence for emission from a 'A,- state; the range of P values
(degree of polarization) observed ( + 0.35-0.40) following excitation into the main
' B , + 'A, absorption band indicated that the emitting state had mainly ' B ,
character. 565 An interesting study of the temperature and viscosity dependence of
the fluorescence spectra and polarization of 1-naphthol, indole, 1-naphthonitrile,
and 1-naphthylamine has been interpreted in terms of electronic level inversion
effects made possible by the closeness of the two low-lying ' L aand ' L , states.566
Rotational-diffusion parameters and root-mean-square displacements and rotation
angles were extracted from the data. The polarization of the emission from an
intermolecular excimer in a fluid solution has been observed.567 The excimer
emission from propylene glycol solutions of 9-anthroic acid was found to have a
negative polarization, indicating that it has out-of-plane character. The excimer is
formed between two hydrogen-bonded dimers, and the polarization value suggests
that they do not have a common principal axis. Polarized emission has been
observed from solutions of DNA bases and their nucleosides and n u c l e ~ t i d e s . ~ ~ ~
The very low fluorescence quantum yield of these molecules indicates that their
emission lifetimes are very short ( - 1 ps), much shorter than their likely rotational
relaxation times in room-temperature aqueous solution, and high polarization
values should be observed. This was confirmed experimentally. A related study of
the polarized emission spectra of room-temperature aqueous solutions of CpC
561
B. Valeur and G. Weber, J. Chem. Phys., 1978, 69, 2393.
562
P. Gangola, N. B. Joshi, and D. D. Pant, Chem. Phys. Lett.. 1977, 51, 144.
563
I. M. Gulis and A. I. Komyak, Zh. Prikl. Spektrosk., 1977, 27, 841.
564
I. M. Gulis, A. I. Komyak, and V. I. Tomin, Zzv. Akad. Nauk SSSR, Ser. Fiz., 1978, 42, 307.
565
S. Hotchandani, P. Paquin, and R. M. Leblanc, Can J. Chem., 1978, 56, 1985.
S. Suzuki, T. Fujii, A. Imai, and H. Akahori, J . Phys. Chem., 1977, 81, 1592.
567
S. Suzuki, T. Fujii, and N . Yoshiike, Chem. Phys. Lett., 1979, 62, 287.
568 J. P. Morgan and M. Daniels, Photochem. Photobiol., 1978, 27, 73.
92 Photochemistry
(cytidylyl-3’,5’-cytidine)and CMP (cytidine monophosphate) led to the identifi-
cation of three components which were attributed to monomer and excimer
fluorescence and, unusually, excimer p h o t o p h o r e s ~ e n c ePolarized
.~~~ fluorescence
spectra of room-temperature aqueous solutions of the four DNA bases thymine,
cytosine, adenine, and guanine have also been measured re~ently.’~’The fluores-
cence lifetimes of thymine and cytosine were estimated to be < 2 ps whereas the
lower polarization values for the other two indicated lifetimes of =lops. The
symmetry of vibrational modes active in the fine-structure fluorescence spectrum of
porphyrin and its derivatives has been determined from studies in which there was
selective laser excitation of their isotropic rigid-glass solutions at liquid He
temperatures. 5 7 1 Polarized emission studies have made it possible to identify two
components in the broad, structureless, red emission from four trisdithioketone
complexes of rhodium(m) and iridium(n1) and assign them to d-d and charge
transfer, n-d* states.572 The Stark structure of the absorption and emission
spectra of the rare-earth ions Pr3+, Eu3+, Tb3+, Er3+, and Tm3+ have been
investigated using polarized luminescen~e.~’~
Fluorescence depolarization is an important technique in the study of the
rotational diffusion of molecules (in their excited electronic states), particularly in
biophysical chemistry.574It is clearly important to understand the dynamics of the
interaction of electronically excited states in molecules and their immediate
environment, and some interesting recent papers have considered several aspects of
”’
this problem. Picosecond time-resolved fluorescence anisotropy decay measure-
ments have been used in studies of (0 the rotational diffusion of Rose Bengal in
protic and aprotic solvents,576where a solvent torque model was proposed to
account for deviations from a slip boundary condition, (ii) the long molecule 2,5-
bis(5‘-t-butyl-2-benzoxazolyl)thiophene in cyclohexane and ethanol,’ 77 and (iii)
the mode-locking dye DODCI (3,3-diethyloxadicarbocyanineiodide) in ethanol
and isopropanol. The statistical accuracy of rotational correlation times
obtained from photon-counting pulse fluorimetry has been discussed. 7 9 Phase ’
fluorimetry has been used in studies of the rotational diffusion of Rhodamine 6G in
aqueous and micellar environments and in studies of a series of symmetrical
molecules in propylene
569
M. Daniels and J. P. Morgan, Chem. Phys. Lett., 1978, 58, 283.
570
P. R. Callis, Chem. Phys. Lett.. 1979, 61, 563.
”’ L. A. Bykovskaya, A. T. Gradyushko, R. I. Personov, Yu. V. Romanovsku, K. N. Solov’ev, A. S.
Starukhin, and A. M. Shul’ga, Zh. Prikl. Spektrosk., 1978, 29, 1088.
572
J. T. Merrill and M. K. DeArmond, J . Am. Chem. SOC.,1979, 100, 2045.
573
V. P. Lebedev and A. K. Przhevusku, Fiz. Tverd. Tela (Leningrad), 1977, 19, 2373.
574 For a general review of techniques used in the study of rotational dynamics see G. Williams and
J. Crossley, Annu. Rep. Prog. Chem., Sect. A , 1978, 74, 77.
575 For a brief review of studies of solvation phenomena using fluorescence see T. C. Werner in ‘Modern
Fluorescence Spectroscopy’, ed. E. L. Wehry, Plenum, New York, 1976, Vol. 2, p. 271.
576 K. G . Spears and L. E. Cramer, Chem. Phys., 1978, 30, 1.
577 G. R. Fleming, A. E. W. Knight, J. M. Morris, R. J. Robbins, and G. W. Robinson, Chem. Phys. Lett.,
1977, 51, 399.
”* G. R. Fleming, A. E. W. Knight, J. M. Morris, R. J. Robbins, and G. W. Robinson, Chem. Phys. letf.,
1977, 49, 1.
579
P. Wahl, Chem. Phys., 1977, 22, 245.
U. K. A. Klein and H. P. Haar, Chem. Phys. Lett., 1978, 58, 531.
58’
W. W. Mantulin and G . Weber, J. Chem. Phys., 1977, 66, 4092.
An interesting application of fluorescence polarization has been in the study of
the translational-energy dependence of product rotational energy in chemilumi-
nescent reactions.582The fluorescence polarization of XeBr* (2Z+)produced in the
reaction of Xe ( 3 P 2 )with Br, was found to increase rapidly to a limiting value of + f
as the relative energy of the colliding beams was increased from 0 1 eV. The --+
results showed that the electronic transition involved had AIR = 0 and that the
collisions tend towards spectator stripping dynamics as the energy increases. The
emission anisotropy of the fluorescent molecules 4-amino-4'-nitrosostilbene(ANS)
and 4-dimethylamino-4'-nitrosostilbene (DNS) has been shown to decrease as the
dielectric constant of the solvent increase^.'^' The effect has been interpreted in
terms of the influence of the Onsager reaction field on the volume of the solvent shell.
An apparatus suitable for the measurement of fluorescence polarization at high
pressures has been described and applied to a study of quinine sulphate in
i s o bu tan 0 1 .~~~
Difficult problems arise because of stress effects in the cell windows,
but when overcome this is a valuable method for introducing isothermal viscosity
changes.
Two interesting reviews of circularly polarized luminescence (CPL) measure-
ments in biophysics and biochemistry have appeared and include useful discussions
of the instrumentation involved.585The four parameters A, B, C, and D that
describe the magnetically induced circularly polarized luminescence (MCPL) have
been derived for certain well defined conditions for systems with C , (n > 3 )
symmetry.586 Large errors are introduced if the effects of photoselection and
reorientation are not included in the analysis. A selection rule AM = 0 for elastic
collisions of homonuclear diatomic molecules has been formulated following a
detailed study of the circular polarization ratio of resonance fluorescence doublets
for the v' = 16 level of the 3110u+ electronic state of iodine as a function of
rotational quantum number.587
The Triplet State.-Further developments and applications of a variational-plus-
perturbational method of calculating the triplet states of polyatomic molecules
have been reported.588There are two steps in the method, firstly an SCF calculation
of the triplet state wavefunction in the open-shell one-operator formalism of
Roothaan and secondly a treatment of the electronic correlation of the SCF states
by a second-order perturbation expansion. The method was applied with some
success to calculations of the lower triplet states of a number of aliphatic carbonyl
compounds and six azabenzenes. The method is limited to non-
multiconfigurational triplet states. Other developments in procedures for calculat-
ing triplet-state properties were reported in an earlier section.
582 C. T. Rettner and J. P. Simons, Chem. Phys. Lett., 1978, 59, 178.
583 A. Kawski, J . Kukielski, and J. Kaminski, Z . Naturforsch., Teil A , 1978, 33, 1228.
s84 G . S. Chryssomallis, H. G. Drickamer, and G. Weber, J . Appl. Phys., 1978, 49, 3084.
s85 ( a ) I.Z. Steinberg, Methods Enzymol., 1978,49, 179; ( b ) I. Z . Steinberg, Annu. Rev. Biophys. Bioeng.,
1978, 7, 113.
586 K. W. Hipps, J . Phys. Chem., 1978, 82, 602.
587 S. R.Jeyes, A. J. McCaffery, M. D. Rowe, P. A. Madden, and H. Kato, Chem. Phys. Lett., 1977,41,
550.
( a ) J. Leclercq and J. M. Leclercq, Chem. Phys., 1977, 22, 221; (6) J . Leclercq, P. Yvan, and J. M.
Leclercq, Chem. Phys., 1977, 22, 233.
94 Photochemistry
Ab initio CI calculations of the potential-energy surfaces of the 3Z-, 3A2,3A“,
and 3B, states of the nitrenium ion, NH,’, have been carried The results
will be useful in the interpretation of molecular-beam studies of the reaction of the
N + ion with H,. A suggestion that there is a second triplet state of trimethylene-
methane, C(CH,),, that is energetically accessible from, and of lower symmetry
than, the 3 A , state has not been substantiated by SCF calculations.590 An
interesting study of the influence of geometry on the first triplet-state energy
surfaces of linear polyenes, employing a restricted open-shell Nesbet SCF ab initio
minimal basis set, produces results in agreement with experimental cis-trans
isomerization data.’” An unrestricted Hartree-Fock method has been used to
investigate the first triplet state of methylglyoxal.592The ketonic group was found
to acquire a larger amount of unpaired spin than the aldehyde group. The influence
of substituents and of the crystal field on the triplet spin substates of benzene has
been discussed in terms of a model in which there is coupling between the lower 3b1u
and 3Elu state^."^ The structures and properties of the lowest triplet states in p-
b e n z o q ~ i n o n e , ’p-q~inones,’~’
~~ and benzoquinone ’’~5 have been investigated
theoretically, and variations in the zero-field splitting parameters of the strongly
basic lowest 3(71,11*) states of 174-diaza-aromaticshave been interpreted in terms of
proximity effects and hydrogen-bonded c o r n p l e ~ e s . ’The
~ ~ application of the
Siebrand relation between the phosphorescence lifetime and the triplet-state energy
to chlorophyll and pheophytin has been discussed,598and the influence of a trigonal
distortion on a Jahn-Teller effect in a triplet state has been considered.599
There have been several useful discussions of methods for determining triplet
quantum yields.600
Phosphorescence. An experimental redetermination of the collision-free phos-

phorescence lifetime and quantum yield of the 3B, state of SO,, 8.1 f 2.5 ms and
0.95 f 0.29, respectively, has removed a theoretical anomaly arising from the
previously determined much lower values of these quantities which were incom-
patible with theories of radiationless transitions and estimates from the integrated
,
area of the 3B, + f l A absorption band.601The errors in earlier determinations
arose from pressure saturation effects and the diffusional loss of triplets. The former
can be nicely accounted for by Freed’s recent theory of collision-induced
589 D. M. Hirst, Mol Phys., 1978, 35, 1559.

s90 D. M. Hood, R. M . Pitzer, and H. F. Schaefer, tert., J . Am. Chem. Soc., 1978, 100, 2227.
591 V. Bonacid-Koutecky and S. Ishimaru, J. Am. Chem. Soc.. 1977, 99, 8134.
592 S. F. Abdulnur, J. Am. Chem. Soc., 1978, 100, 6341.
593 P. J. Vergragt and J. H. Van der Waals, Mol. Phys., 1977, 33, 1507.
594 J. H. Lichtenbelt, D. A. Wiersma, H. T. Jonkman, and G. A. Van der Velde, Chem. Phys., 1977, 22,
297.
595 N. J. Bunce, J. E. Ridley, and M. C. Zerner, Theor. Chim. Acta, 1977, 45, 283.
596 C. Mijoule and J. M. Leclercq, J. Chem. Phys., 1079, 70, 2560.
597 A. Chodkowska, A. Grabowska, and J. Herbich, Chem. Phys. Lett., 1977, 51, 365.
5y8 N. N. Lebedev and A. A. Krasnovskii, jun., Biofizika, 1978, 23, 1095.
59y J. M. Dixon, R. Lacroix, and J. Weber, J. Phys. C , 1977, 10, 3793.
6oo (a) R. Bensasson, C. R. Goldschmidt, E. J. Land, and T. G. Truscott, Photochem. Photobiol., 1978,28,
277; ( b ) S. A. Lee, J . Chem. Phys., 1978, 68, 602; (c) R. Bensasson and E. J. Land, Photochem.
Photobiol. Rev.,1978, 3, 163.
601
F. Su, J. W. Bottenheim, D. L. Thorsell, J. G. Calvert, and E. K. Damon, Chem. Phys. Lett., 1977,49,
305.
intersystem crossing.602The luminescence observed following laser excitation of
the li3A2-Z1A band of thiophosgene has been attributed to resonance phosphores-
~ e n c e . ~Accurate
” measurements of the phosphorescence lifetime of benzene in the
temperature range 2-30 K have supported earlier microwave-induced phos-
phorescence studies, which concluded that the emission was predominantly from
the upper two-spin substates of E l , symmetry,604and measurements of this 3Blu
state lifetime for benzene in Ne, Ar, and Kr matrices of varying thicknesses have
demonstrated experimentally the effect of nearby surfaces on the rate of radiation-
less transitions.605
A re-examination of the time-resolved emission from benzophenone under
isolated molecule conditions has shown that the decay is a single exponential,
z x p, and comprises hot phosphorescence and diluted fluorescence.606The
molecule was found to conform to the intermediate level structure case, and
contrary to earlier suggestions there is strong scrambling of the vibronic states in
the (IT>} manifold due to anharmonic coupling. Sharp changes in the quantum
yield of phosphorescence from low-pressure vapours of aromatic carbonyl
compounds have been observed as the excitation energy is increased in the region of
the onset of the S2 (m*) absorption band,607and the phosphorescence of xanthone
in n-hexane solutions has been found to be strongly temperature-dependent and has
been attributed both to a change in the excited-state ordering6’* and to a
configurational change.609 A study of the temperature dependence of the
phosphorescence of bicyclic enones revealed discontinuities in the Arrhenius plots
which probably arise from the freezing out of torsional motions by the solvent cage,
which lead to radiationless decay routes.610 The theory of the quantum beats
observed in the phosphorescence of [’HI ,]tetrarnethylpyrazine, and example of an
aza-aromatic system where the principal axis of the zero-field splitting tensor does
not coincide with the local symmetry axes of the dominant spin-orbit coupling on
the nitrogen nucleus, following the application of a n/2 microwave pulse resonant
with the z,-z, transition, has been given in terms of the Feynman, Vernon, and
Hellwarth model of the Schradinger equation.61 A combination of an applied
magnetic field, which lifts the degeneracy of the lowest triplet state, and selective
dye-laser excitation of the m, - 1 level has made it possible to observe differences in
both the spin substates’ phosphorescent lifetimes and their chemical reactivity in a
single crystal of dimethyl-s-tetrazine.61
The vibrational structure in the phosphorescence of phenanthrenequin~ne~’and
in seven monohalogen-substituted phenylacetylenes’ l 4 has been anaIysed. In the
‘02 F. Su,F. B. Wampler, J. W. Bottenheim, D. L. Thorsell, J. G. Calvert, and E. K. Damon, Chem. Phys.
Lett., 1977, 51, 150.
603 J . R. Lombardi, J. B. Koffend, R.A. Gottscho, and R.W. Field, J. Mol. Spectrosc., 1977, 65, 446.
‘04 N. G . Kilmer and A. H. Kalantar, Chem. Phys. Lett., 1977, 48, 274.
‘05 S. S. Hasnian, P. Brint, T. D. S. Hamilton, and I. H. Munro, Philos. Mug., 1977, 36, 629.
606 D. Zevenhuijzen and R. Van der Werf, Chem. Phys., 1977, 26, 279.
607 T. Itoh, H. Baba, and T. Takemura, Bull. Chem. SOC.Jpn., 1978, 51, 2841.
‘08 R. E. Connors and P. S. Walsh, Chem. Phys. Lett., 1977, 52, 436.
‘09 V . G. Klimenko, E. A. Gastilovich, and D. N. Shigorin, Zh. Fiz. Khim., 1978, 52, 2962.
‘Io S. W. Beavan and D. Phillips, Mol. Photochem., 1977, 8, 31 1 .
‘I1
R.A. Schadee, J. Schmidt, and J. H. Van der Waals, Mol. Phys., 1978, 36, 177 (see reference 406).
B. Dellinger, R. M. Hochstrasser, and A. B. Smith, tert., J. Am. Chem. SOC.,1977, 99, 5834.
613 E. A. Gastilovich, T. S. Kopteva, and D. N. Shigorin, Opt. Spektrosk., 1978, 44, 900.
614 H. Singh and J. D. Laposa, J. Lumin., 1978, 16, 257.
96 Photochemistry
latter study two vibrational subspectra were identified; the first, which was
dominant in the spectrum of the parent compound, phenylacetylene, involved
totally symmetric vibrational levels of So, whereas the second, whose relative
contribution increased with the mass of the halogen, involved b , , out-of-plane,
vibrational levels of So. There have been interesting reports of conditions that make
it possible to observe room-temperature phosphorescence in fluid solutions 6 1 and
in dried deposits.616A theoretical investigation of the mechanism of the external
heavy-atom quenching process has been published; in it phosphorescence lifetime
data is used from a series of compounds in which the position of an external halogen
atom is rigidly fixed relative to a benzene or naphthalene chromophore by being
attached at various positions around a bicyclic [2.2. llheptane framework.61 An
example of such a compound is the monobromonaphthonorbornene (6). The study
Br
suggests that the effect is electronic in origin. The heavy atom introduces a number
of singlet charge-transfer states by electron transfer from the perturber to unfilled
n* orbitals of the chromophore. These states mix with the triplet states of the
chromophore through a second-order mechanism involving one-centre spin-orbit
coupling terms. The results should be compared with those of a study of the internal
heavy-atom effect given in reference 412.
Phosphorescence Polarization. The nature of the lowest triplet states and the
mechanism of phosphorescence in a series of linear polynuclear p-quinones have
been investigated using measurements of the phosphorescence spectrum, lifetime,
and polarization.618 It was found that linear annellation (addition of further
benzene rings) produced either of two regular changes in the nn* and nn* states,
depending on whether or not the addition increased or decreased the difference in
the number of rings on either side of the quinoid ring. The negative polarization of
the phosphorescence from the three isomeric hydroxypyridines and 2-meth-
,oxypyridinein EPA (5 : 5 : 2 ethyl ether, isopentane, ethyl alcohol) supports the idea
that the lowest triplet state is nn*.619 A change in the polarization of 4-
hydroxypyridine on going to alkaline EPA was attributed to the lowering of the ' B ,
state energy to take it below that of the 'A 1, the lowest state in all other cases. There
has been a series of investigations of the polarized phosphorescence spectra of
6's N. J. Turro, K. C. Liu, M. F. Chow, and P. Lee, Photochem. Photobiof., 1978, 27, 1 .
A, K. Chandra, N. J . Turro, A. L. Lyons, jun., and P. Stone, J . Am. Chem. SOC.,
1978, 100,4964.
'I8 M. Nepras and A. Novak, Collect. Czech. Chem. Commun., 1978, 42, 2343.
619
S. Hotchandani and A. C. Testa, J. Chem. Phys., 1977, 67, 5201.
Spectroscopic and Theoretical A spec ts 97
chlorophyll and chlorophyll-like molecules published.620A study of the polarized
phosphorescence of a 4-carboxybenzophenone and of benzophenone-3,3’,4,4‘-
tetracarboxylic acid dianhydride in poly(methy1 methacrylate) glasses at room
temperature has shown clearly that molecular motion is not responsible for the low
value of P observed when the ketone phosphorescence is monitored following
-
excitation of the singlet nn* absorption.621Direct excitation of the strong T , + So
absorption in the second compound gave a P value of 0.5, showing that there is
no significantrotational depolarization during the lifetime of the triplet state (2 ms).
The first measurements, using phosphorescence depolarization, of segmental
relaxation times in bulk polymer systems have been reported in a study of
poly(methy1 acrylate) containing copolymerized acenaphthylene or 1-vinyl-
naphthalene as probe molecules.6 2 2 The activation energies of the observed
relaxation processes were in excellent agreement with published values obtained
using established techniques such as dielectric relaxation.
Optically Detected Magnetic Resonance (0.d.m.r.) and Related Techniques.
Spin-lattice relaxation (SLR) rates of phosphorescent triplet states in zero field
(ZF) can be measured by optically detected magnetic resonance (0.d.m.r.)
techniques. Details of measurements using a more direct, purely optical method
have been given in which the SLR rates of the lowest triplet state of 9,lO-
anthroquinone in Shpolskii matrices were obtained from the phosphorescence
decay profile following pulsed excitation.623Another technique which can give the
magnetic and optical parameters usually obtained from 0.d.m.r. measurements, but
in the absence of perturbing radiofrequency or microwave fields, is illustrated in a
study of the 3(nn*)state of three benzophenones oriented in single crystals of 4,4’-
dibromodiphenyl ether at 1.6K.624The technique involves the measurement of the
signs, magnitudes, field positions, and widths of the changes in the phosphorescence
intensity induced by a magnetic field and which have their origin in level-
anticrossing and cross-relaxation effects. The method can give information on the
fine-structure, g , hyperfine, and quadrupole tensors of emitting paramagnetic
species.
An 0.d.m.r. study of crystalline biacetyl and a microwave-saturation
recovery, microwave-induced delayed phosphorescence (MIDP), and 0.d.m.r.
study of crystalline glyoxal and [2H2]glyoxa1626have shown that the z spin
sublevel, which is along the C-0 bond direction, is the dominant radiative decay
channel in these a-dicarbonyls. A strong temperature dependence of the spin
sublevels’ origin of the phosphorescence of the thioketone xanthione has been
found in an 0.d.m.r. At high temperatures (77K) the T,z(nn*) sublevel is
620 ( a ) S . S. Dvornikov, V. N. Knyukshto, A. N. Sevchenko, K . N. Solov’ev, and M. P. Tsvirko, Dokl.
Akad. Nauk SSSR. 1978, 240, 1457; (b) A. T. Gradyushko, S. S. Dvomikov, K. N. Solov’ev, and
M. P. Tsvirko, Zzv. Akad. Nauk SSSR, Ser. Fiz., 1978,42,511; ( c ) A . T. Gradyushko, K. N. Solov’ev,
and M. P. Tsvirko, Opt. Spektrosk., 1978,44, 1123.
621 R. Loutfy and M. A. Winnik, J . Phys. Chem., 1978, 82, 1304.
622 (a) H. Rutherford and I. Soutar, J . Polym. Sci., Polym. Phys. Ed., 1977, 15,2213; ( b ) H. Rutherford
and I. Soutar, J . Polym. Sci., Polym. Lett, Ed., 1978, 16, 131.
623 R. Avarmaa and A. Suisalu, Chem. Phys. Lett., 1977, 52, 567.
624 J . A. Mucha and D . W. Pratt, J . Chem. Phys., 1977,66, 5356.
625 I . Y. Chan and S. Hsi, Mol. Phys., 1977, 34, 85.
I . Y. Chan and K. R. Walton, Mol. Phys., 1977, 34, 65.
A. H. Maki, P. Svejda, and J . R. Huber, Chem. Phys., 1978, 32, 369.
98 Photochemistry
the principal source of the short-lived red emission, but at low temperatures the ISC
process preferentially populates the T , x and T,y sublevels, and the phosphores-
cence originates from them instead. A study of the emission wavelength dependence
of the ZF splitting parameters of the triplet state of the amino-acid tryptophan and
several of its derivatives has revealed strong discontinuities, illustrated in Figure 26,
nm
25000 24000 23009 22000-,

cm
Figure 26 Relationship between the phosphorescence of indole (in n-butanol at 1.3 K ) and the
zero-jield triplet-state transition I B E I with its relative linewidth as afunction of the emission
‘,
wavelength. The I B E 1 transition was scanned at 15 MHz s- and the values shown in the
graph are obtained by sweeping toward higher frequency. The diference in I D-E Ifor sweeps
made toward lower frequency is on the average about 45 MHz, except when monitored in the
409-41 5 nm region of the phosphorescence spectrum; otherwise the 1 D-E I transition
frequency may be assigned at any particular wavelength of emission by subtracting
approximately 23 MHzfrom the values of the curve datapoints. The wavelength region where
this procedure is invalid is the region of overlap between the 0-Q and lower-energy vibrational
bands of the phosphorescence. Here the 0.d.m.r. ‘line’gradually ‘broadens’ until finally it is
resolved into a distinct doublet
which in previous studies of tryptophan phosphorescence in horse-liver alcohol

dehydrogenase and in hen egg-white lysozyme (two and six tryptophan residues,
respectively) have been attributed to contributions from tryptophans in different
sites.628The present study shows that such interpretations must be made with
caution and implies that the optical and 0.d.m.r. lines of tryptophan are
inhomogeneously broadened. 0.d.m.r. measurements have contributed to a study
of the triplet states of NAD’ and NADH in which, by making comparisons with
model compounds, it was shown that the phosphorescence arises predominantly
from the adenine base.629The symmetry and geometry of the lowest excited triplet
states of quinoxaline and p-dichlorobenzene have been determined from a
combined 0.d.m.r. and proton-ENDOR 0.d.m.r. studies have been
628
A. L. Kwiram, J . B. A. Ross, and D. A. Deranleau, Chem. Phys. Lett., 1978, 54, 506.
629 J. B. A. Alexander, K . W. Rousslang, A. G. Motten, and A. L. Kwiram, Biochemistry, 1979,18,1808.
630 C . Von Borcyzyskowski, M. Plato, K . P. Dinse, and K. Moebius, Chem. Phys., 1978, 35, 355.
reported of the triplet states of chlorophyll b molecules, 6 3 1 of the chlorophyll
protein 668,632of chlorophyll d i m e r ~and ~ ~palladium p ~ r p h i nA. study
, ~ of ~ ~ ~ of
zinc etipporphyrin has illustrated the point that the absolute rate constants for
individual triplet sublevels can be obtained from measurements of the
phosphorescence- and the fluorescence-detected o.d.m.r., an emission intensity,
and the phosphorescence quantum yield.635
The origins of the large variations in the magnetic and dynamic properties of the
3n71* states of aromatic carbonyls have been explored in a combined 0.d.m.r. and
MIDP study of substituted 1-indanones and related molecules.6 3 6 Substantial
differences in the T , properties of the 1-indanones and benzaldehydes were found
which were attributed to lower spin-orbit coupling matrix elements between 3n71*
and 37171* states in the indanones relative to those in benzaldehydes, and to a
reduced direct mixing of 3n7r* and 37r7r* states in the indanones due to their more
rigid planar structure. Zeeman PMDR measurements on duraldehyde have shown
that a consistent model of the results can be achieved by including an S , T , ISC
process, where T , is an HCHO-like n7r* state, in addition to an S , + T , ISC
process.637Estimates of the vibronic mixing coefficients indicate that the T , state
has x 20% m*character. Intramolecular heavy-atom effects in 9,lO-dichlorophen-
anthrene and 1,2,3,4-tetrachloronaphthalenehave been investigated using PMDR
techniques,638 and a MIDP study of p-H,C,(CN), and a number of its charge-
transer complexes has shown that the shortening of the phosphorescent lifetime in
the latter arises from a change in the non-radiative decay constant of the shortest-
lifetime MIDP studies of the triplet states in pyrazine640 and p-
xylene 6 4 1 have also been reported.
Electron Spin Resonance (e.s.r.).The effects which arise in e.s.r. experiments on the
photoexcited triplet states of aromatic molecules because of phase coherence
between individual spin sublevels have been described,642 and a theoretical
treatment of rotary echoes in photoexcited triplet states has been published.643 A
study of the photoexcited triplet states in tetraphenyl chlorin and magnesium
tetraphenyl porphyrin using a light-modulated e.s.r. technique have indicated that
the electron spin polarization signals previously observed from chlorophylls in vitro
arise from the chlorin ring.644 A fast laser-flash e.s.r. technique has been used to
determine the triplet spin sublevel decay rates in Rhodopseudomonas
~ ’ of 6500 s- for k , and k, and 1800 s- fork,, which compare
~ p h a e r o i d e s . ~Values
R. H. Clarke and H. A. Frank, Chem. Phys. Lett., 1977, 51, 13.

632 R. H. Clarke, W. R . Leenstra, and W. G . Hagar, FEBS Lett., 1979, 99, 207.
633 R. H. Clarke, D. R. Hobart, and W. R . Leenstra, Semicond. Insuf., 1978, 4, 313.
h34 J. A. Kooter, G. W. Canters, and J. H. Van der Waals, Mol. Phys., 1977, 33, 1545.
635 W. R. Leenstra, M. Gouterman, and A. L. Kwiram, J . Chem. Phys., 1978, 68, 327.
636 S. Nuzuma and N. Hirota, J . Phys. Chem., 1979, 83, 706.
637 A. Campion and M. A. El-Sayed, NBS Spec. Publ. (US.), 1978, 526, 271.
638 T. Akasheh, Chem. Phys. Lett., 1978, 59, 392.
639 M. Yogi, N. Nishi, M. Kinoshita, and S. Nagakura, Mol. Phys., 1978, 35, 1369.
640 K. Matsuzaki and T. Azumi, J . Chem. Phys.. 1978, 69, 3907.
641 P. J. Vergragt, J . A. Kooter, and J . H. Van der Waals, Mol. Phys., 1977, 33, 1523.
642
J. Schmidt, J . Lumin., 1979, 18/19, 183.
643 M . E. Tarrasch and C. B. Harris, Chem. Phys., 1979, 37, 293.
644 E. Nissani, A. Scherz, and H. Levanon, Photochem. Photobiol., 1977, 25, 93.
645 P. Gast and A. J. Hoff, FEBS Lett., 1978, 85, 183.
100 Photochemistry
favourably with values obtained from previous 0.d.m.r. and optical experiments,
were obtained.
Single Vibronic Level (SVL) Studies.-Experiments in which single vibronic levels
(SVLs) in ‘small’ polyatomic molecules can be selectively excited with narrow-band
tunable dye-laser radiation continue to provide invaluable information on the
photophysical and photochemical properties of molecules. The events following
selective excitation can conveniently be monitored by fluorescence excitation
spectroscopy, fluorescence lifetime measurement, resonance fluorescence emission
spectroscopy, and the appearance of photoproducts. A few of the more interesting
SVL studies are reported on here; others appear elsewhere in this chapter and in the
next chapter.
A brief review of the scope of SVL studies and the results of recent investigations
h a s a ~ p e a r e d . ~study
~~A ofthe A ’ A , +- %‘Al transitionin [‘H2]-, [1Hl,2Hl]-,and
[2H2]-formaldehyde has revealed marked variations in the collision-free SVL
radiative and non-radiative lifetimes, k , and kNR,re~pectively.~~’ The results show
that the v4 out-of-plane bending mode is the inducing mode for radiative transitions
and is a promoting mode for non-radiative transitions, [an earlier SRVL (single
rovibronic level) study has already indicated that the v6 mode is also a promoting
mode for non-radiative transitions],648and they are in qualitative agreement with
recent theoretical work, It was also clear from the results that the variations in the
SVL k, and k,, values for [‘H,]formaldehyde were significantly greater than those
for [lH,, 2Hl]- and [2H2]-formaldehyde. The first measurements of the absolute
values of &(K’,J’) have been reported for a number of SRVLs of the 4l vibrational
state of the 2’A , electronic state of H,CO and D2C0.649The results showed that
there was no systematic variation of & (K’,J’)with J’ within a given K‘ manifold but
that there was a clear trend of the J’-population averaged ,$F value to lower values
with increasing K ’ . The vibronic-level dependence of the photodecomposition of
H 2 C 0 ( R I A , ) has been investigated by monitoring the red chemiluminescence of
HNO* (2”’‘) formed in the reaction of NO with H atoms produced in the
reaction 6 5 0 H 2 C 0 + hv --* H + HCO. The results revealed vibronic features in
the H-atom quantum yield, &, versus excitation wavelength dependence despite
the possibility that the presence of 10 torr of NO might obscure such effects via
collisional vibrational relaxation. The onset for the radical formation reaction was
found to be at x 330 nm. The quantum yield, &,then increased smoothly towards
lower wavelengths until anomalously low values were found for the 2’4’ and 2443
levels that appear just below 300nm. The HNO* @‘A’’) state has itself been the
subject of an SVL The fluorescence lifetimes of the (011) and (010) levels,
extrapolated to zero pressure, were found to be 8 - 4 + 2 1 and 7.4 t 2 ps, respect-
ively. These values when compared with the natural lifetime of 5 ps itstimated from
the oscillator strength suggest that the non-radiative decay processes from this state
are negligible.
646
E. K . C. Lee, Acc. Chem. Res., 1977, 10, 319.
64’
R. G. Miller and E. K. C. Lee, J . Chem. Phys., 1978, 68,4448.
648 K. Y. Tang, P. W. Fairchild, and E. K. C. Lee, J . Chem. Phys., 1977,66, 3303.
649 K . Shibuya and E. K . C. Lee, J . Chem. Phys., 1978,69, 5558.
“O
K . Y. Tang, P. W. Fairchild, and E. K. C. Lee, J . Phys. Chem., 1979,83, 569.
651
F . Yamada, T. Ishiwata, M. Kawasaki, K. Obi, and I. Tanaka, Chem. Phys. Lett., 1979, 61, 518.
A laser-induced fluorescence study of glyoxal in which a 454.5 nm Ar + laser line
with 0.1 & 0.02 cm- bandwidth was used to excite a few rotational levels in the 0,O
band of the S , + So ( ' A , + 'A,) absorption band has shown that the emission
contains identifiable fluorescence from a number of isolated single rotational
levels.6s2 No evidence was found for a dependence of the collision-free emission
yield on the K',J' quantum numbers. The vibronic level dependence of the
photodissociation of glyoxal to give CO has been i n ~ e s t i g a t e d . ~The' ~ CO
produced, following selective excitation of the (Oo, 7', 5l, 8172,8'4') SVLs in the
' A , state, was monitored using 147 nm resonant emission. All of the levels exhibited
significant pressure and vibronic dependencies which were interpreted by a model in
which dissociation occurred from vibrationally excited levels in the 3A, state
reached by collisionally induced ISC during which vibronic specificity is preserved.
This latter requirement is compatible with theoretical treatments of collisionally
induced ISC since the 3A, state level density p at the energies of the initially
populated 'A, levels is small enough to be characteristic of small molecule
behaviour. A remarkable experiment has demonstrated for the first time the
phenomenon of intramolecular quantum beats from a polyatomic molecule.6s4In
the experiment a very-low-temperature beam of biacetyl molecules produced in a
pulsed nozzle expansion of a biacetyl-helium mixture into a vacuum was excited to
single rovibronic states in the first singlet state by 1 cm-' bandwidth pulsed,
tunable, dye-laser radiation. The time-resolved fluorescent decay showed strong
rotational-state-dependent oscillatory behaviour which can be understood in terms
of the coupling of S , , T , , and So levels. The beats are not susceptible to Doppler
broadening and therefore provide a spectroscopic tool which is complementary to
Lamb dip and two-photon measurement techniques.
New measurements of the SVL dependence of & in the ' B 2 , state of p -
difluorobenzene 6 s s and of rF in the ' B 2 , state of naphthalene have resulted in
significant revisions of earlier measurements. The new p-difluorobenzene study
used continuous, as opposed to pulsed, excitation, and the naphthalene study was
performed on very-low-termperature beams from a pulsed nozzle, as opposed to a
room-temperature vapour.
The dye-laser excited SVL fluorescence spectra from several vibrational levels in
the 'nn* ('B3,) excited state of pyrazine have been reported.6s7 The fluorescence
spectra show intense progressions of a non-totally symmetric vibration (1 Oa,b,,)
not found in benzene or pyrimidine SVL fluorescence spectra, and this is consistent
with the idea that the excited-state potential is distorted along the direction of this
out-of-plane mode. There have been several measurements reported of the
fluorescence decay of pyrimidine -660 and methyl-substituted pyrimi-
dines6" that show clearly the two components (fast, z FZ Ins, and slow,
"' C. S. Parmenter and B. F. Rodorf, Chem. Phys., 1978, 27, 1.

653
G. H. Atkinson, M. E. McIlwain, and C. G. Venkatesh, J . Chem. Phys.. 1978, 68, 726.
654 J . Chailen, T. Benson, M. Gurnick, and J. D . McDonald, Chem. Phys. Lett., 1979, 61, 195.
655 L. J . Volk and E. K. C. Lee, J . Chem. Phys., 1977, 67, 236.
656 F. M. Behlen, N . Mikami, and S. A. Rice, Chem. Phys. Lett., 1979, 60,364.
''' Y. Udagawa, M. Ito, and I. Suzuka, Chem. Phys. Lett., 1979,60, 2 5 .
K . G . Spears and M. El-Manguch, Chem. Phys., 1977, 24, 65.
659 K. Uchida, I. Yamazaki, and H. Baba, Chem. Phys., 1978, 35, 91.
660 H. Reineccius and H. Von Weyssenhoff, Chem. Phys. Lett., 1977, 52, 34.
Table 6 Comparison of intermediate decay parameters*
Relative Experimental
Molecule energy cm - v,, x 104cm-1 pT x 10-3cm N NVsT x lo3 p,(exp)/p;(calc.)
G1yoxal 0 5.1 0.3 0.46 0.23 5.3
926 2.2 2.1 4.4 1.o 15
Methylglyoxal 0 1.6 2.7 3.8 0.62 10
1076 0.64 18.4 27 1.7 12
2084 0.34 70 110 3.7 8.2
Biacetyl 0 0.23 130 175 4.0 12
1011 0.15 300 420 6.3 2.7
Pyrimidine 0 5.8 0.92 5.6 3.2 115
1012 3.1 6.1 73 23 113
2024 1.8 18.4 226 41 55
* The data for glyoxal, methyglyoxal, and biacetyl were obtained from refs. ( a H c ) .The p i is the vibronic density. Values are selected to show the range of parameters for those
states that have larger than gas kinetic self quenching. This is the ‘black hole’ region defined by ref. (c).
(a) R. van der Werf, E. Schutten, and J. Kommandeur, Chem. Phys., 1976, 16, 151. ( b ) R. van der Werf, E. Schutten, and J. Kommandeur, Chem. Phys., 1975,11, 281.
( c ) R. van der Werf and J. Kommandeur, Chem. Phys., 1976, 16, 125.
z x 40 ns) expected for intermediate-case molecules. The observed decreases in the
fluorescence yield of the slow component on methyl substitution and on increasing
the excitation energy are readily understandable in terms of the increasing numbers
of triplet vibronic levels effectively coupled to the fluorescent singlet level. The data
for molecules in which a quantitative analysis of dual fluorescence decays has been
undertaken, i.e. pyrimidine and the dicarbonyls glyoxal, methylglyoxal, and
biacetyl, are collected together in Table 6. The strong pressure dependence of the
lifetime of the slow component has been discussed,661and the SVL fluorescence
lifetimes of several vibronic levels of s-triazine have been measured.662
5 Intermolecular Photophysical Excited-state Decay Processes

As in my last report I have selected only a few papers of general interest for this
section. A more comprehensive coverage of these topics appears in later chapters.
Electronic-energy Transfer.-A number of interesting theoretical papers have
considered the problem of determining the distribution of end-to-end distances in
flexible-chain molecules from measurements of the efficiency of energy transfer
between donor, D, and acceptor, A, molecules attached to the chain ends. This
problem is of particular interest in studies of polymers and biopolymers where
electronic-energy transfer is frequently used as a spectroscopic ‘ruler’ despite the
often considerable uncertainty associated-with the interpretation of the results. In a
discussion of the fluorescence decay kinetics of such molecules it has been
established by Monte-Carlo-type calculations on the chains Tyr-(Ala),-Tyr
( n = 4 or 9) that an assumption that the distances between D and A are not
correlated with the relative orientations of D and A is indeed valid and is even
adequate for chains where the conformations are dominated by entropic factors.663
This results in a considerable simplification of the integral equation for the
luminescence decay because terms involving both the distance of separation and the
relative orientation may be separated. The orientation factor, K , can then be
calculated from an available analytical expression. The validity of this assumption
was established both for unperturbed chains in which there are no long-range
interactions and for chains where there are stacking interactions.664 The resulting
theory was subsequently used in a study of natural polypeptide chains.665A related
paper has considered an extension of this problem to the case of energy transfer
which involves transitions of mixed polarization characterized by two or three
transition moments.666 Earlier work had considered only the orientational
dependence of energy transfer for transitions with single electric-dipole transition
moments. The study shows that for cases where the orientations of the chromo-
phores are fixed but unknown the error in the calculated ‘energy-transfer’ distances
is smaller when the fluorescence polarizations of D and A are reduced and is
unlikely to exceed 10% for polarizations <0.3. It was also shown that errors
661
P. R . Nott and B. K . Selinger, Aust. J . Chern.. 1978, 31, 1875.
662
P. R . Nott and B. K . Selinger, Ausr. J . Chem., 1978, 31, 1889.
663
A. Englert and M. Leclerc, Proc. Natl. Acad. Sci. USA, 1978, 75, 1050.
664
M. Leclerc, S. Premilat, and A. Englert, Biopofymers, 1978, 17, 2456.
665
M. Leclerc, S. Premilat, and A. Englert in ‘Peptides: Proc. of the Fifth American Peptide Symposium’,
ed. M. Goodman and J. Meienhofer, Wiley, New York, 1977, p. 364.
666
E. Haas, E. Katchalski-Katzin, and I. Z. Steinberg, Biochemistry, 1978, 17, 5064.
104 Photochemistry
arising from restrictions in the orientational freedom of the chromophores which
have been stressed by other authors were of little importance. In contrast to
examples of the dynamic averaging of relative orientations it is possible to conceive
of a situation where there is a continuous stationary statistical orientational
distribution of D,A pairs. The energy-transfer properties of systems exhibiting such
static averaging have been compared with those where dynamic averaging is
applicable.667
The effect of electronic-energy transfer on the luminescence properties of one-
dimensional systems, e.g. some molecular crystals, has been shown to be very
different from that found for two- and three-dimensional systems (which are
themselves different).668 This result may provide the basis of a method for
determining the dimensionality of systems where energy transfer is taking place in
which the concentration dependence of the fluorescence anisotropy or quantum
yield is measured. The functioning of the photosynthetic unit has been modelled by
computer-simulated energy transfer on a two-dimensional random lattice.669The
effect of the chlorophyll donor concentration and the chlorophyll/trap ratio on the
trapping rate were investigated. In general the time dependence of the trapping rate,
and of the related chlorophyll fluorescence decay, was not a simple exponential, in
qualitative agreement with recent experimental observations. The fluorescence
decay was found to decrease substantially as the chlorophyll concentration was
increased. The study clearly illustrates that a Foerster-type energy-trapping or
'hopping' mechanism can account for the rapid trap excitation observed in the
photosynthetic unit. The origin of the excitation intensity dependence of the in vivo
photosynthetic unit fluorescence lifetime has been satisfactorily explained in terms
of a biomolecular singlet exciton annihilation process.670* 6 7 1 A further develop-
ment of recent discussions of long-range energy transfer in systems where both the
donor and acceptor can diffuse has resulted in approximate expressions for the time
dependence of the donor fluorescence in one-, two-, and three-dimensional
systems.672 The expressions are sufficiently different to allow in principle a
distinction to be made between the behaviour of microscopic chemical or biological
systems of different dimensionality as proposed above (reference 668) for the
analogous steady-state fluorescence properties. A new concept of convolution
kinetics has been discussed in which the time dependence of the fluorescence for
systems undergoing energy transfer can be calculated from a measurement of the
decay function for an excitation pulse of negligible duration.673Expressions for the
time-dependent emission from a random one-dimensional system in which there are
a number of energy-transfer mechanisms operating 6 7 4 and expressions for the
excitation intensity-dependent non-linear luminescence quenching in liquid and
solid systems where the effects of both separation distance and diffusion on the
energy-transfer process have been considered 6 7 5 have been published.
667 R . E. Dale, Acfa Phys. Pol. A , 1978, 54, 743.
"* C. Bojarski, Acta Phys. Acad. Sci. Hung., 1978, 44, 217.
h69 J . A. Altmann, G. S. Beddard, and G . Porter, Chem. Phys. Lelt., 1978, 58, 54.
670 G . S. Beddard and G . Porter, Biochim. Biophys. Acta. 1977, 462, 63.
671 G. Paillotin, C. E. Swenberg, J . Breton, and N. E. Geacintov, Biophys. J . , 1979, 25, 513.
672 U . Gosele, Spectrosc. Left., 1978, 18, 445.
673 M . Hauser, R. Frey, U . K . A. Klein, and U . Gosele, Acfa Phys. Chem., 1977, 23, 21.
674 T. Holstein, S. K. Lyo, and R. Orbach, J . Lumin., 1979, 18/19, 634.
675 S. F. Kiiin, M . S. Mikhelashvili, and I. M. Rozman, Izv. Akad. Nauk SSSR, Ser. Fiz., 1978,42,414.
An interesting discussion of electronic-energy transfer in multicomponent
luminescent systems has appeared which is valuable in understanding the behaviour
of, for example, the mixed dye solutions used as active media in dye lasers.676The
theoretical expressions for this process of sensitized photoluminescence require that
both the absorption and emission spectra and the quantum yield of each
component be known. The theory was applied successfully to a mixture of 7-
diethylamino-4-methylcoumarin, 3,6-diamino- 10-methylacridinium chloride
hydrochloride, and Rhodamine 6G dyes. Theoretical treatments of sensitized
fluorescence in molecular crystals 6 7 7 and of the localization of electronic excitation
energy in isotopically mixed organic crystals, where a ‘critical’ concentration effect
on the energy-transfer process has recently been identified,678have been published.
Electronic-energy transfer studies in polymer photochemistry 6 7 9 and those
involving transition-metal co-ordination compounds 680 have been reviewed.
Two noteworthy experimental studies should be mentioned at this point. A
recent investigation of electronic-energy transfer from the shortlived S, state of
Rhodamine 6G to the ground state So of the fluorescent dye 2,5-bis[5’-t-butyl-2-
benzoxazolyl]thiophene (BBOT) has raised an interesting and important question
concerning the Foerster-Dexter theories of such energy-transfer processes.68 As
originally formulated these theories consider the case of resonant transfer from a
thermally equilibrated vibronic manifold { FjD> of the donor-acceptor pair. The
authors show that this can readily be extended to the case where the vibrational
relaxation in a metastable state of the S, vibronic manifold is slow relative to the
rate of electronic relaxation from the state, provided that the emission spectrum
used in the overlap integral is that of the donor’s initially prepared non-equilibrated
state SnD{V;} (n > 1). For intermediate cases where the vibrational relaxation is
neither very fast nor very slow then the equations become time-dependent, and the
usual expressions for the transition probability cannot be applied in a straightfor-
ward manner. The experiments were performed by populating the rhodamine’s S ,
electronic state using sequential two-photon laser excitation and monitoring the
enhancement in the fluorescence intensity of BBOT at 430 nm compared with the
intensity when the rhodamine and BBOT were separately present. The results were
analysed to give an estimate for the lifetime of the metastable S, state of rhodamine
of ~ 3 . 1 0 - sl ~ and a quantum yield for S, -+ So fluorescence of
(2.1 & 0.5) Finally, mention must be made of a quite remarkable
demonstration of time-resolved electronic-energy transfer in a study of the
light-harvesting mechanism in the red alga Porphyridium cruentum.682The alga
contains three main accessory light-harvesting pigments in structures known
as phycobilisomes, which are attached to the thylakoid membrane
containing the chlorophyll a. The absorption spectra of these pigments form a
sequence as follows: B-phycoerythrin (56 1 nm), R-phycocyanin (622 nm), allophy-
cocyanin (651 nm), chlorophyll a (680 nm). The corresponding sequence of
676 J. Kusba and C. Bojarski, J . Lumin., 1979, 20, 73.
67’ V. M . Kenkre, Chem. Phys., 1979, 36, 377.
678
J . Klafter and J . Jortner, Chem. Phys. Left., 1979, 62, 9.
679 J . E. Guillet, Pure Appl. Chem., 1977, 49, 249.
P. Natarajan, J. Sci. Ind. Res., 1977, 36, 256.
68’ I. Kaplan and J . Jortner, Chem. Phys., 1978, 32, 381.
”’ G . Porter, C. J. Tredwell, G. F. W. Searle, and J. Barber, Biochim. Biophys. A d a , 1978, 501, 232.
106 Photochemistry
emission spectra made it possible to design an experiment in which the first member
was selectivelyexcited and the picosecond time-resolved fluorescence emission from
each of them separately measured. The result reproduced in Figure 27 shows clearly
a sequential energy transfer in the expected order.
0
0
00
0
0
0
0 I I I I I I I
0 50 100
picot cco n d
Figure 27 The risetimes of wavelength-resolved pigment fluorescence in P. cruentum. Each
curve was measured separately with interference filters as wavelength selection filters and
aligned on the time axis. BPE is B-phycoerythrin, RPC is R-phycocyanin, APC is
allophycocyanin, and C H L is chlorophyll a. Fluorescence intensity is on a normalized linear
scale.
(Reproduced with permission from Biochim. Biophys. Acta, 1978, 501, 232)
In the theoretical description of triplet-triplet energy transfer of Dexter there is

no explicit account of electron spin, but clearly the spin quantization of the donor
will be transferred intact to the acceptor when resonance transfer occurs. If the
donor and acceptor molecules are rotated with respect to each other then a given
spin state in the donor will populate a mixture of spin states in the acceptor with the
overall effect on the triplet manifold of a basis transformation. A paper has
investigated the effects of such a transfer between translationally inequivalent sites
on the spin-coherence properties of a system as shown in free induction decay, echo
decay, and spin-locking decay experiments.683 The spin-lock signal in localized
impurity states in molecular crystals is known to be comparable to the triplet
lifetime and should therefore be a suitable technique to study the transfer process,
the other two processes having much shorter characteristic times. Similarly, spin
coherence measurements in rigid glassy media should be suitable to study the
energy-transfer process and obtain a value for the average rate constant for
exchange particularly between like species. A value for the asymptotic quantum
yield of triplet energy transfer has been found by calculating the fraction of acceptor
molecules with energy above the minimum energy for decomposition after allowing
a statistical energy distribution among the internal energy modes of the collision
683
H . C . Brenner, J. C . Brock, and C . B. Harris, Chern. Phys., 1978, 31, 137.
complex.684Energy-transfer quenching processes involving an exchange mechan-
ism have been treated by an extension of the Marcus-Weller theory and applied to
available experimental data on energy transfer from aromatic triplets to biacetyl
and to O - a n i ~ i l . ~ ~ ~
Singlet-state Quenching.-A sequence of papers has considered the problem of
partly diffusion-controlled reactions in which there is a competition between a
chemical or physical process and the physical process of diffusion. In particular the
problem of fluorescence quenching is considered where a particular manifestation
of this competition is known, namely, the consistently lower values of cr', the
reaction distance, calculated from time-resolved quenching experiments compared
with those from steady-state experiments.686This discrepancy is illustrated by the
results in Table 7 for the fluorescence quenching of 1,2-benzanthracene by CBr,. As
Table 7 Values of cr and D which give the bestjts to decay curves vrom Nemzek and
Ware) and to steady-state experiment of I ,2-benzanthracene quenched by
CBr, in propanediol
o'/A D/ 1O6 cm2 s - '
CBr, concentration/moldm- 15 "C 25 "C 35 "C 15°C 25°C 35°C
From decay curves
0.098 9.0 8.5 8.5 0.23 0.50 0.88
0.18 9.0 9.0 8.0 0.24 0.44 0.95
0.29 8.0 7.0 7.0 0.28 0.66 1.1
Steady-state experiments (classical model)
11.2 - - 0.287 - -
Steady-state experiments (our model)

8.8 8.8 8.8 0.37 0.59 1.01
a first attempt to account for this discrepancy a simple model was proposed in
which there are two reaction regions surrounding an activated molecule A*:
(i) A region between r = cr, the collision distance of fluorophore and quencher,
and r = d,the reaction distance in which the effective reaction rate constant
is infinite. The concentration of the quencher B in this region is zero and there
is, therefore, no diffusion of B.
(ii) The region r > cr' in which there is no reaction but there is a net diffusion of B
towards the boundary, r = cr'.
It can be seen that on the basis of this model the static effect, in which A*,B pairs
where cr < rB < cr' instantly disappear, will not be observed in time-resolved
experiments but will contribute to steady-state experiments. As shown in Table 7
the inclusion of this static term results in excellent agreement between the cr' values
calculated using the two experimental methods. This simple model was sub-
sequently developed to consider the competition between the true chemical rate of
reaction and the diffusion of the reactants.687The later model assumes that k(r),the
rate constant at r , has a constant value k for cr < r < cr' and is negligible for
'" I. Oref, Int. J. Chem. Kinet., 1977, 9, 751.

V. Balzani and F. Bolletta, J. Am. Chem. SOC.,1978, 100, 7404.
J. C. Andre, M. Niclause, and W. R. Ware, Chem. Phys., 1978, 28, 371
J. C. Andre, M. Bouchy, and W. R. Ware, Chem. Phys., 1979, 37, 103.
108 Photochemistry
r > o’. This is more appropiiate to short-range processes such as Dexter-type
electronic energy transfer, but the model could accommodate any process for which
k(r) is known, e.g. Foerster-type energy transfer. The variation of k(r) with r leads,
as in the simple model, to two distinct regions:
( i ) A region, o < r < o’,where there is chemical reaction with rate constant k
but no diffusion.
(ii) A region, r > o’,where there is net diffusion towards the barrier at r = o’
but no chemical reaction.
This model leads to an expression for the apparent rate constant of the reaction,
k,(t), which can be used to obtain equations applicable to time-resolved and steady-
state fluorescence quenching experiments. These equations were then applied
successfully to the analysis of the fluorescence intensity and polarization changes
observed in experiments on the quenching of pyrene, sulphorhodamine G, and 1,4-
bis[2-(5-phenyl)oxazolyl]benzene (POPOP) fluorescence by biacetyl, I - ,and CBr,,
respectively.668The approach taken in these papers leads to a general improvement
in the level of the interpretation of quenching experiments compared with the usual
crude separation into static and dynamic terms.
The above treatment is restricted to uncharged particles as it does not consider
terms arising from the diffusion of charged particles in the electric potential around
A*. An important contribution to the general problem of the recombination of
charged particles has been published recently and can be directly applied to
fluorescence quenching involving charged species. An analytical solution to the
time-dependent Smoluchowski equation with Coulomb potential and a general
boundary condition, i.e. the boundary can range between perfectly absorbing and
perfectly reflecting, has been obtained and used to obtain expressions for the
distribution function, reaction rate, and survival probability.689 The theory
represents the extension to the transient case of the well known result of Debye for
the steady-state reaction rate with a Coulomb potential interaction. The result is
used to solve the continuum model for diffusion-controlled reactions where there is
an initial Boltzman distribution of particles, and it is shown that the leading terms in
the reaction-rate expression are formally the same as the result of Smoluchowski for
no long-range forces but with the sum of hard-core radii replaced by an effective
encounter distance.690 The expressions for the decay of the fluorescence intensity
IF(f)and the steady-state quenching rate constant, k,, are given in equations (17),
where 01 = l/zo + 47rDApQ and fi = 4A2pQ(nD)+, and (18), where zo is the
Idt) = constant x exp( - at - 2j?t+), (17)
k~ = 4dDT0 + 4nki2(ko)+ (18)
unquenched fluorescence lifetime, D the sum of diffusion coefficients of the
fluorophore and quencher, A the effective encounter distance at which the reaction
proceeds with certainty, and pa the mean quencher concentration. It will be
interesting to compare the values of these parameters with those of the model for
uncharged species mentioned above. A timely paper has pointed out a number of
600 J. C.Andre, M. Bouchy, and W. R.Ware, Chem. Phys., 1979, 37, 119.
689 K. M. Hong and J. Noolandi, J. Chem. Phys., 1978, 68, 5163.
690 K. M. Hong and J. Noolandi, J. Chem. Phys., 1978,68, 5172.
difficulties which arise in the interpretation of steady-state fluorescence quenching
experiments in micellar systems.691It is shown that the time dependence of the
quencher distribution can significantly alter the value of the detergent-aggregation
number calculated from the quenching results. The cases of ‘mobile’ and ‘immobile’
quencher distribution can significantly alter the value of the detergent-aggregation
not exchange with the surrounding solvent, respectively? on the time-scale of the
quenching process.
Triplet-state quenching.-A continuation of the theme in the previous section
concerning the competition between, for example, a quenching reaction and
diffusion may be found in an interesting paper on the temperature dependence of
the ratio of delayed monomer and delayed excimer fluorescence following
triplet-triplet annihilation in fluid media. 6 9 2 A model which included two
annihilation processes was found to reproduce the experimental temperature
dependence in solutions of pyrene in ethanol with realistic parameters. The first
process was a simple solvent cage encounter to give excited monomer ‘M* or
excimer ‘D* from the reactions 3M* + 3M* + ‘D* and 3M* + 3M* +
‘M + ‘M*, full allowance being made for the possibility of re-encounter in the
second reaction using a Noyes-type treatment to give additional excimer fluores-
cence. As formulated by the authors this process alone was unable to account for
the temperature dependence. The second annihilation process included in the
analysis involved a long-range mechanism whose probability falls off exponentially
with distance and thus can be associated with a Dexter-type exchange interaction.
The success of the model combining these two processes indicates that a long-range
interaction could be taking place, but as the authors point out distance de-
pendencies other than an exponential may possibly be equally successful. The
underlying assumptions in this and earlier treatments of triplet-triplet annihilation
have been discussed. 6 9 3 The author suggests that the contribution of re-encounters
to the intensity of delayed excimer fluorescence could usefully be investigated in
anisotropic media such as a phospholipid bilayer where the solute diffusion is
essentially in a plane. Very large values of the excimer/monomer delayed
fluorescence intensity ratio can be anticipated in such media. The nature of the
interaction which results in delayed fluorescence emission from the encounter
complex formed by two triplet excited species has been discussed. 694 The roles of
charge-transfer and excimer states were both considered.
6 Photochemical Excited-state Decay Processes

The pressure of a limited space for this chapter has resulted in this section being
unusually brief. Important developments under this heading will be reported on in
more detail in the next appearance of this chapter (Volume 13).
Theories of Photochemistry.-A discussion of the application of semi-empirical
theoretical methods to the static aspects of photochemistry, which involve the
’” P. P. Infelta, Chem. Phys. Lett., 1979, 61, 88.

’” P. R. Butler and M. J. Pilling, J . Chem. Soc., Furaduy Trans. 2 , 1977, 73, 886.
693
K. R. Nawvi, Chem. Phys. Letr.. 1978, 54, 49.
694 B. F. Minaev, Izv. Vyssh. Uchebn. Zaved., Fiz.. 1978, 21, 12.
110 Photochemistry
construction of potential-energy hypersurfaces, has appeared.6 9 5 The discussion is
illustrated by considering the photochemical processes of excited-state proton
transfer and the reaction pathways of electrocyclic reactions. A review has
discussed the photochemical heavy-atom effect (to be contrasted with the more fully
documented photophysical heavy-atom effect),696and the application of heavy-
atom methods to the determination of photochemical reaction multiplicity has been
critically examined.697The use of energy differences to explain solvent effects on
photophysical processes has been a n a l y ~ e d , ~ and ” a model for ab initio calcu-
lations of the effects of solvent molecules on the excited states of solute molecules
has been presented. 699 The barriers which arise in excited-state potential-energy
suffacesfrom the avoided crossings between MOs of identical symmetry have been
calculated for an H abstraction in the formaldehyde-methane system, 700 and the
selection rules for photochemical excited-state decay processes which involve the
crossing or avoided crossing of hypersurfaces have been discussed using an
adiabatic quantum-mechanical treatment. 701 The rate constants for the transfer
across the barriers which arise from the crossing of potential-energy surfaces have
been shown to exhibit a non-Arrhenius temperature dependence. 702
A discussion of reversible photophysical processes such as thermally activated
delayed flourescence and intramolecular energy transfer has appeared in which
general kinetic relations and methods for evaluating the thermodynamic para-
meters of the processes are derived.703A valuable review of the theory of the time
evolution of excited molecular states has been published,704and the calculation of
the thermochemical properties of atoms and molecules in specific quantum states
and in thermal and non-thermal distributions over specific groups of quantum
states has been A review of the ‘sudden polarization’ effect mentioned
earlier in this report has been p ~ b l i s h e d , ” ~and a set of consistent terms and
definitions to describe primary photochemical and energy-transfer processes has
been proposed.707 A strategy to transform red light into blue light has been
proposed and demonstrated experimentally. 708 In the scheme red-light-absorbing
sensitizers lead to a reaction in a dioxetan in which the excited carbonyl fragments
produced transfer their energy to sensitizer states that emit blue light. Chemi-
ionization and -excitation processes which are important in gas lasers and plasma
69s J . Michl, Mod. Theor. Chem.. 1977, 8, 99.

696
J . C. Koziar and D . 0. Cowan, Acc. Chem. Res., 1978, 11, 334.
697
F. A. Carroll, Mol. Photochem., 1977, 8, 133.
698
G. Hug, Chem. Phys. Lett., 1978, 55, 695.
699 G. G. Hall and C. J . Miller, Jerusalem Symp. Quantum Chem. Biochem., 1977, 10, 373.
700 A. Devaquet, A. Sevin, and B. Bigot, J . Am. Chem. SOC.,1978, 100, 2009.
70’ J . C. Lorquet, C. Galloy, M. Desouter-Lecomte, M . J . Decheneux, and D . Dehareng, Jerusalem Symp.
Quantum Chem. Biochem., 1977, 10, 397.
702 J . P. Laplante and W. Siebrand, Chem. Phys. L e t f . , 1978, 59, 433.
’03 J . B. Birks, Nouv. J . Chim., 1977, 1, 453.
’04
S. Mukamel and J. Jortner in ‘Excited States’, ed. E. C. Lim, Academic Press, London, 1977, Vol. 3,
p. 57.
705 W. C. Gardiner, jun. and R . D. Levine, J. Chem. Phys., 1978, 68, 4524.
706 J . Koutecky, V. Bonacic-Koutecky, J . Cizek, and D. Doehnert, Int. J. Quantum Chem., Quanfum
Chem. Symp., 1978, 12, 357.
707
G. B. Porter, V. Balzani, and L. Moggi, Adv. Photochem., 1974, 9, 147.
708 N. J . Turro, D. Brewer, W. Farneth, and V. Ramarnurthy, Nouv. J . Chim., 1978, 2, 85.
chemistry have been discussed in a paper on energy-transfer processes between
excited states.709
A new non-equilibrium approach to the calculation of chemical rate processes in
condensed media has been proposed which represents a fundamental departure
from the equilibrium-rate theories which derive from Eyrings transition-state
theory.710 In the new reactive complex theory of photochemical reactions a
photoactivated reactive complex is either deactivated or reacts to produce the
primary photochemical products. The theory has been applied to recent picosecond
time-resolved studies of photofragmentation reactions in condensed media, e.g.
solutions of iodine in organic solvents. An equally interesting development in the
theory of photochemical reactions has been described in which excited-
state-ground-electronic-state energy separations are minimized by determining
which molecular motions convert electronic into vibrational en erg^.^
Photochemical reaction pathways can be predicted by considering the extent of
localized electronic excitation within a molecule. An extension of the rules of Lin
(1966) to encompass a greater number of photochemical reaction types has been
p r ~ p o s e d . ~The
' application of the rules to a number of reactions was discussed,
including those of Woodward-Hoffmann-type and reactions involving spin
inversion.
The application of semi-empirical SCF MO methods to investigations of the
mechanisms of organic photoreactions has been re~iewed,~'and the application of
a qualitative theoretical LCFC (linear combination of fragment configurations)
approach to such studies has been proposed '14 and has been illustrated by studies
of, for example, spin inversion in triplet photochemical reactions. 7 1 The appli-
cation of various topicity rules to a number of bond-rupture reactions has been
confirmed following the calculation of the associated correlation diagrams using
semi-empirical methods. The efficiencies of photochemical triplet cycloaddition
and hydrogen-abstraction reactions have been discussed. The discussion
highlights the point that any inefficiency may have its origin prior to the formation
of any reaction intermediates.
The importance of intermediates of biradicaloid geometry in the photochemical
reactions of organic molecules has been r e ~ i e w e d , ~and the electronic structures
of the excited-state diradical and zwitterionic intermediates have been discussed
using as a basis localized natural orbitals.719There has been a growing recognition
in recent years of the importance of reactions which proceed via upper excited
states. Such reactions are often exposed by a strong dependence of the reaction
pathway on excitation wavelength. This topic has been reviewed recently 7 2 0 and
log A. Ricard, J . Phys. (Paris), Colloq., 1977, 239.

710 D. J. Diestler and F. K . Fong, J . Am. Chem. SOC.,1978, 100, 1992.
711 H. E. Zimmerman and M. G. Steinmetz, J . Chem. SOC.,Chem. Commun., 1978, 230.
712 T. Lee, J . Am. Chem. SOC.,1977, 99,3909.
'I3 M . J. S. Dewar, Faraday Discuss. Chem. Soc., 1977, 62, 197.
714 N. D. Epiotis and S. Shaik, Prog. Theor. Org. Chem., 1977, 2, 348.
715 S. Shaik and N. D: Epiotis, J . Am. Chem. SOC.,1978, 100, 18.
'I6 E. M. Evleth and E. Kassab, J . Am. Chem. SOC.,1978, 100, 7859.
N. J. Turro and V. Ramamurthy, Mol. Photochem., 1977, 8, 239.
7La J. Michl, Photochem. Photobiol., 1977, 25, 141.
7'9 K. Yamaguchi and T. Fueno, Chem. Phys., 1977, 23, 375.
720 N. J. Turro, V. Ramamurthy, W. Cherry, and W. Farneth, Chem. Rev., 1978, 78, 125.
112 Photochemistry
discussed with particular reference to the photochemistry of a number of
cyclobutenes. 7 2 1 Photochemical reactions that may involve either valence shell or
Rydberg-like states have been discussed for a number of simple organic mole-
cules. 7 2 2 An interesting theoretical investigation has provided evidence for the
existence of electronic selection rules in the photochemical reactions of transition-
metal complexes.723Orbital and state correlation diagrams were used to analyse
the stereochemistry of photoinduced substitution reactions of chromium (111)
complexes. The initial loss of a ligand was followed by an isomerization process and
then by the nucleophilic attack of an entering ligand.
Photoionization and Photodetachment.-The problem of calculating the effects of
electron correlations on photoionization cross-sections and vacancy decay rates
has been reviewed,724as have the recent theoretical models of calculating inner-
shell photoionization cross-sections. 7 2 5 The proceedings of a NATO Advanced
Study Institute meeting on photoionization and other probes of many-electron
interactions have also been published. 7 2 6 Procedures for calculating photoioniz-
ation cross-sections which involve the absorbing boundary method,727the ground-
state inversion potential method,728the recently developed Extended Koopmans
Theorem,729and a Stieltjes-Tchebycheff procedure, which makes it possible to
perform the calculations in Hilbert space,730have all been discussed in the recent
literature. Excitations which accompany photoionization have been treated using
many-body Rayleigh-Schrodinger perturbation theory,73 and a selection rule for
parity-unfavoured transitions has been determined for the photoionization of
linear molecules.732Parity favouredness has been used to explain the asymmetry of
the angular distribution in the photoionization of diatomic molecules,733and the
behaviour of the photoionization cross-section in the vicinity of a resonance has
been discussed.734Two models of laser photoionization have been published, the
first of which considers a one-dimensional single bound-state square well as a
model 7 3 5 and the second a two-level atom.736
Atoms. The photoionization of atomic systems 7 3 7 and the selective photoioniz-
ation of atoms using laser radiation 7 3 8 have been the subjects of valuable reviews.
”’ ( a )J . Michl, A . Castellan, M. A. Souto, and J . Kolc, Jerusalem Symp. Quantum Chem. Biochem., 1977,
10, 361; (b) see for example M. A . Souto, J . Kolc, and J . Michl, J . Am. Chem. Soc., 1978, 100, 6692.
C. Sandorfy, Prog. Theor. Org. Chem., 1977, 2, 384.
’*’
lZ2
L. G. Vanquickenborne and A. Ceulemans, J . A m . Chem. SOC.,1978, 100, 475.
lZ4 H. P. Kelley, J . Phys. (Paris), Cofloq.,1978, 16.
725
F. C. Farnoux, J . Phys. (Paris), Colloq., 1978, 64.
lZ6 NATO Advanced Study Institute Series, ed. F. J. Wuilleumier, Plenum, New York, Vol. B18, 1976.
727 S. Nordholq, J . Electron Spectrosc. Relat. Phenom.. 1979, 15, 109.
P. R . Hilton: S. Nordholm, and N. S. Hugh, J . Chem. Phys., 1977, 67, 5213.
lZ9 D. M. Chipman, Int. J . Quantum Chem., Symp., 1977, 11, 365.
730 P. W . Langhoff, Int. J . Quantum Chem., Symp., 1977, 11, 301.
73’ I . Hubac and V. Kvasnicka, Croat. Chem. Acta, 1977, 49, 677.
732 N. Chandra, J. Phys. B., 1977, 10, L489.
733 E. S. Chang, J. Phys. B, 1978, 11, L293.
734 A. F. Starace, Phys. Rev. A , 1977, 16, 231.
735 A. Goldberg and B. W. Shore, J . Phys. 8, 1978, 11, 3339.
736 J. R. Ackerhalt, Phys. Rev. A , 1978, 17, 293.
737 P. G. Burke in ‘Atomic Processes and Applications’, ed. P. G. Burke and B. L. Moiseiwitsch, North-
Holland, Amsterdam, Netherlands, 1976, p. 199.
738 V. S. Letokhov, V. 1. Mishin, and A. A. Puretskii, Prog. Quantum Electron., 1977, 5, Pt. 3, 139.
An investigation of the resonant ionization of atoms by an intense electromagnetic
wave has resulted in an expression for the resonance width which is valid for light
pulses of arbitrary intensity, duration, and shape.739A paper has considered the
interaction that occurs between the radiative decay of an excited atomic state and a
possible autoionization decay mode of the state.740 The interaction can affect the
excitation profile of the excited state, its fluorescence yield, and the spectra of the
emitted photons and electrons. Significant effects on the alignment of ions in atomic
photoionization have been found when many-electron correlations are included in
calculations,741 and a new model for double photoionization has been proposed
which involves configuration mixing between a double ionization continuum and
an inner-shell excitation ionization channel, thus avoiding the necessity of an
intermediate autoionizing state.7 4 2 The appearance of quantum beats in the
ionization signal from an alkali-metal atom has been treated theoretically by
considering a coherent superposition of the D3/2,5/2fine-structure levels.743In the
treatment the levels are excited by a two-photon resonant pulse and subsequently
photoionized by a delayed probe pulse.
Of the numerous experimental investigations of atomic photoionization mention
is made only of a few studies of photoionization in the presence of an electric field
because of their wider interest in relation to laser-induced selective ionization. Such
studies are exemplified by two recent studies of the photoionization of rubidium
atoms in which narrow field-dependent resonance structures were observed. 745 7449
Attention has been drawn recently to similarities between spectral effects and non-
linearities in the photoionization of atoms in d.c. discharges by low-intensity light
and in the breakdown of gases with high-intensity lasers. 746 Interesting observ-
ations have been made in experiments on Rydberg atoms which are consistent with
there being photoionization of such highly excited atoms by 300K background
blackbody radiation.747
Molecules. A number of modifications to the orthogonalized-plane-wave ap-
proximation used to calculate molecular photoionization cross-sections have been
suggested, 748 and a considerable improvement in the agreement between experi-
mental photoionization cross-sections and those calculated using the plane-wave
method can be brought about by assuming the photoelectron's energy equals that
of the incident photon.749A two-centre treatment has been used to calculate the
photoionization cross-sections for the ui = 0-14 vibrational levels of the X'C,,ui,
state of hydrogen for a range of photon energies,75oand the breakdown of the
73')
M . V. Fedorov, J . Phys. B, 1977, 10, 2573.
740
L. Armstrong, jun., C. E. Theodosiou, and M . J . Wall, Phys. Rev. A , 1978, 18, 2538.
741
E. G. Berezhko, V. K. Ivanov, and N. M . Kabachnik, Phys. Lert. A , 1978, 66, 474.
742
J . P. Connerade, J . Phys. B, 1977, 10, L239.
743 A. T. Georges and P. Lambropoulos, Phys. Rev. A , 1978, 18, 1072.
744 R. R. Freeman, N. P. Economou, G . C. Bjorklund, and K . T. Lu, Phys. Rev. Lert., 1978,41, 1463.
745 S. Feneuille, S. Liberman, J. Pinard, and P. Jacquinot, C. R . Hebd. Seances Acad. Sci., Ser. B, 1977,
284, 291.
746 N. S. Kopeika, G. Eytan, and A. P. Kushelevsky, J . Appl. Phys., 1979, 50, 1 1 .
747
E. J. Beitung, G. F. Hildebrandt, F. G . Kellert, G. W. Foltz, K. A. Smith, F. B. Dunning, and R . F.
Stebbings, J . Chern. Phys., 1979, 70, 3551.
"* T. Fujikawa, T. Ohta, and H. Kuroda, J . Electron Spectrosc. Refat. Phenorn., 1979, 16, 285.
749
M. 3. M. Beerlage and D. Feil, J . Electron Spectrosc. Relat. Plienom.. 1977, 12, 161.
750 H. Tai and M . R . Flannery, Phys. Rev. A , 1977, 16, 1124.
114 Photochemistry
independent particle, MO, picture of ionization has been demonstrated in a study of
the photoionization of the valence electrons of carbon monosulphide, phosphorous
mononitride, and diphosphorus, using a two-particle-hole approximation.7 5
Some very interesting experimental studies of the photoionization of van der
Waals molecules and clusters have been published. Measurements of the photo-
ionization efficiency curves for several heteronuclear rare-gas van der Waals
molecules have amongst other things made it possible to determine the potential
energy of the excited molecular Rydberg state at a distance which corresponds to
the equilibrium interatomic distance of the ground-state van der Waals mole-
c ~ l e . ~The
’ ~ proton affinities of water and hydrogen fluoride have been
determined in a study of the photoionization of the corresponding dimeric
molecules,7s3and the proton affinity of ammonia and the proton solvation energies
by more than one NH, molecule have been measured in similar studies using this
molecular beam-photoionization method. 5 4 An interesting comparison has been
published of the photoionization energies of neutral and ionic species on going from
the gas phase to the liquid phase.755For the change from gas to liquid phase the
values for neutral species exhibit a 1-2eV red shift and for charged species a
2-3 eV blue shift.
Multiphoton Ionization. A number of papers on both the theoretical and experi-
mental aspects of multiphoton ionization have appeared in the published proceed-
ings of an international conference.756A dressed-atom model for the calculation of
multiphoton ionization rates has been extended by the inclusion of continuum as
well as bound atomic states,7s7 and a method for deriving rate equations from
Bloch equations known as the Wilcox-Lamb method has been illustrated by
considering both two- and three-level atom cases.7s8 In the latter study the
differences between the cases of copropagating and counterpropagating laser
excitation beams were discussed. A perturbation theory approach to the calculation
of multiphoton ionization cross-sections of complex atoms has been proposed and
illustrated by calculations on the helium atom. 59 Semiclassical expressions for the
radiative collision-induced two-photon ionization of atoms have been derived. 7 6 0
The results indicate that the process will provide a sensitive method of studying
radiative collisions.
The apparent disagreement between some of the experimental and theoretical
aspects of laser multiphoton ionization and which has raised the possibility that
such processes are sequential multi-step processes has been The
unusual intensity dependences of laser-induced molecular multiphoton ionization
75’ 1. Schirmer, W. Domcke, L. S. Cederbaum, and W. Von Niessen, J . Phys. B, 1978, 11, 1901.
752 C. Y. Ng, P. W. Tiedemann, B. H. Mahan, and Y. T . Lee, J . Chem. Phys., 1977,66, 5737.
753 C. Y. Ng, D. J. Trevor, P. W. Tiedemann, S. T. Ceyer, P. L. Kronebusch, B. H . Mahan, and Y . T. Lee,
J . Chem. Phys., 1977, 67, 4253.
754 S. T. Ceyer, P. W. Tiedemann, B. H. Mahan, and Y . T. Lee, J . Chem. Phvs., 1979, 70, 14.
755 L. Nemec, L. Chia, and P. Delahay, Can. J . Chem., 1977, 55, 1820.
756 ‘Multiphoton Processes’, ed. J . H. Eberly and P. Lambropoulos, Wiley, New York, 1977 (publ. 1978).
757 S. Chu and W. P. Reinhardt, Phys. Rev. Lett., 1977, 39, 1195.
758 J . R. Ackerhalt and B. W. Shore, Phys. Rev. A , 1977, 16, 277.
75y B. Ritchie, Phys. Rev. A , 1977, 16, 2080.
7h0
M. H. Nayfeh and M. G . Payne, Phys. Rev. A , 1978, 17, 1695.
76’ A. P. Kushelevsky and N. S. Kopeika, IEEE J . Quantum Electron., 1977, 13, 737.
processes have been nicely illustrated in a recent study using a K r F excimer laser
(249 nm) for excitation and a time-of-flight mass spectrometer for detection.762
Photodetachment. Accurate calculations of the photodetachment cross-section of
the hydride ion, H-, that use a perturbation-variation method have been
published.763 A simpler approach to the calculation of this quantity has been
proposed in which a discrete-basis-set expansion is used to represent both the
ground and the continuum states of the system.764An extended asymptotic model
for the calculation of photodetachment cross-sections for alkali anions has been
proposed in which certain assumptions are made regarding the form of the alkali-
anion valence orbital and the alkali-anion 1-wave continuum states.765
Photodetachment energies for the amidogen, NH, - , 7 6 6 and silylene, SiH, - 7 6 7
anions have been calculated using large basis sets, and the photodetachment cross-
section of the fluoride ion, F- ,has been calculated using a Stieltjes imaging method
which involves discrete basis functions only.768It has been pointed out that a beam
of completely polarized electrons can be obtained from an experiment in which the
negative ions of the halogens suffer photodetachment by a beam of circularly
polarized light.769For the photodetachment of I - near threshold the process may
be represented as in equation (19). The first observations of resonances in the
h v + I - ( p 6 lS,) --+ (I+e, lP1) + I(%,Z, 1,2)+e(2s,,2) (19)
photodetachment cross-section of a molecular negative ion at threshold have been
made in a study of the acetophenone enolate anion.770The widths of the resonances
(0.7-0.8nm) gave a lower limit for the lifetime of the autodetaching state of
10- l 3 s. Resonances have also been observed in the photodetachment cross-
sections of the alkali-halide negative ions NaCl - , NaBr - , and NaI - , well above
threshold.771
Electron Transfer.-A recent analysis of experimental values for the rate constants
of excited-state electron-transfer quenching reactions has shown that there are
serious disagreements with the predictions of the well known model due to Marcus
( 1956).772The theory of a new method for investigating reversible excited-state
electron-transfer reactions has been presented.773In the technique simultaneous
measurement is possible of the thermal back-electron-transfer rate constant and the
probability of detectable excited-state electron transfer per quenching encounter.
The possible importance of an abnormal orbital interaction in excited-state
electron-transfer reactions has been and in connection with electron-
transfer processes in biological systems such as occur in photosynthesis and
7h2 S. Rockwood, J. P. Reilly, K. Hohla, and K . L. Kompa, Opt. Commun., 1979, 28, 175.
7h3 A. L. Stewart, J . Phys. B, 1978, 11, 3851.
764 M . A. C. Nascimento and W. A . Goddard, tert., Phys. Rev. A , 1977, 16, 1559.
7 6 5 G. Lamm, A. Szabo, and S. A. Adelman, Phys. Rev. A , 1978, 17, 238.
7 6 h M . M. Heaton, J . Chem. Phys., 1977, 67, 2925.
lb7
M.M . Heaton, J . Chem. Phys., 1977, 67, 5396.
l h A T. N. Resagno, C. F. Bender, and B. V. McKoy, Phys. Rev. A , 1978, 17, 645.
7hy
A. R. P. Rau, Phys. Letr. A , 1978, 64, 367.
7 7 0 A. H. Zimmerman and J. I . Brauman, J . Chem. Phys., 1977, 66,5823.
77’ S. E. Novick, P. L. Jones, T. J . Mulloney, and W. C . Lineberger, J . Chem. Phys., 1979, 70, 2210.
7’2 M . T. lndelli and F. Scandola, J . Am. Chem. Soc., 1978, 100, 7733.
7 7 3 C. A . Wight, tert., T. J. Turley, and J. N. Demas, J . Chem. Phys., 1978, 68, 5486.
7 7 J S. Inagaki and Y . Hirabayashi, Chem. Lett., 1978, 135.

116 Photochemistry
oxidative phosphorylation an interesting development of the vibronic coupling
theory of electron tunnelling between molecules has been proposed.775In the latter
study it has been pointed out that the model that describes vibronically coupled
tunnelling defines directly the characteristics of a weak charge-transfer optical
absorption band whose oscillator strength will be a measure of the tunnelling
matrix element and of the distance between the sites exchanging an electron. The
absorption band therefore provides a critical test of the tunnelling theory.
The role of light-induced electron-transfer reactions of polypyridine-
ruthenium(i1) complexes in the conversion and storage of solar energy has been
and it has been pointed out that the luminescence of ions in solidscan
be quenched by an electron-transfer mechanism.777There have been theoretical
and experimental investigations of the luminescence of intramolecular charge-
transfer states. The existence of twisted intramolecular charge-transfer states in p -
Me2NC,H,CN has been explored in an investigation of the dual fluorescence of
this molecule,778and a through-bond interaction between the ground state and the
polar excited state has been proposed to explain the observation of charge-transfer
emission from bichromophoric systems where the chromophores are separated by
three a - b ~ n d s . ~A~nanosecond
' laser flash photolysis investigation of excited
charge-transfer systems in polar solvents has indicated that an exciplex formed
immediately after the charge transfer is an important intermediate in determining
the subsequent decay processes,78oand an interesting observation of resonance
charge transfer from a photoexcited donor state has been r e p ~ r t e d . ~In
" the latter
study, excited sodium atoms were the donors, and the acceptor states were excited
states of protons and other rare-gas ions. The acceptor excited states gave rise to
intense spontaneous emission in the vacuum U.V.region.
Photoisomerization.-An interesting review has examined the potential for the
storage of solar energy in stable organic photo isomer^.^^' A number of criteria
must be satisfied by a successful system in particular, availability of the chemicals
on an industrial scale, and the kinetic stability of the products. Developments in the
spectral sensitization of isomerizable substrates and the use of heterogeneous
photosensitizers are also discussed. The lowest energy paths for the trans-cis
conversion in the lowest excited states of di-imide have been calculated by three
different SCF-type methods using two different basis sets. 7 8 3 Methods of calcu-
lation have also been compared in a related study of the thermal and photochemical
interconversion of di-imide N-oxide. 84 An ab initio CI calculation was performed
initially using only configurations found to be important in large CI calculations for
a number of fixed configurations, and the results were then compared with those
from less accurate techniques, namely CI limited to single excitations, rigid
J . J . Hopfield, Biophys. J . , 1977, 18, 31 I .
"' N. Sutin, J . Photochem., 1979, 10, 19.
775
17' G. Blasse, Chem. Phys. Lett., 1978, 56, 409.

778 D . J . Cowley, P. J . Healy, and A. H . Peoples, J . Phofochem., 1978, 9, 240.
779 P. Pasman, J . W. Verhoeven, and T. J . De Boer, Chem. Phys. Lett., 1978, 59, 387.
180 H . Masuhara, T. Saito, Y . Maeda, and N. Mataga, J . Mol. Struct., 1978, 47, 243.
781 N. Dutta, R. Trach, D. Frohlich, C. L. Tang, H. Mahr, and P. L. Hartman, Phys. Rev. L e f t . ,1979,42,
175.
782 G. Jones, jun., S. Chiang, and T. X. Phan, J . Phorochern., 1979, 10, 1.
7*3 R . Cimiraglia, J . M. Riera, and J. Tomasi, Theor. Chim. Acta, 1977, 46,223.
784 R . Cimiraglia, M . Persico, and J . Tomasi, Chem. Phys., 1977, 24, 251.
excitations to virtual orbitals, and half electron methods. The results indicate that
the excited-state mechanism, and probably that of the ground state too, involves a
rotation about the N-N bond and not an in-plane inversion. INDO-SCF CI
calculations on the trans-cis isomerization of azomethane in the ground state and in
several low-lying excited states have been published.785 They show that for
1*3(n,n*)states the isomerization proceeds via the rotation of both methyl groups
about the N=N bond. A CIPSI-PCILO method has been used to investigate
theoretically the photochemical cis-trans isomerization of s-trans-l,3-
~ e n t a d i e n eIt. ~was
~ ~found that excitation of either of the isomers resulted in the
equiprobable formation of two allylmethylene intermediates. The first of these
intermediates can lead to isomerization and the second to the starting isomer
following radiationless decay. An interesting PPP-SCF-CI calculation of the
potential surface of the 'phantom' photochemical singlet state of stilbene (see
reference 257) has supported the idea that the state is ' A , and shows that it lies 1 eV
above the lowest absorption band and that it exhibits a minimum for the
perpendicular conformation.787 The calculations were also performed for the
related diphenylpolyenes Ph(CH=CH), (n = 1-5).
Of the numerous experimental studies of photoisomerization mention is made of
only a few. An interesting study of the D isotope effect and the effects of methyl
substitution and excitation wavelength on the photochemistry of 1,3-butadiene has
been published.788A study of the picosecond dynamics of the photoisomerization
of protonated 11-cis retinylidene Schiff bases has shown them to be different from
those in rhodopsin (reported elsewhere in this v o l ~ m e )89, ~and sub-picosecond
spectroscopic techniques have been used to study the dynamics of intramolecular
motion in the excited state of both trans- and ~is-stilbene.~~' A series of papers has
examined in detail the cis-trans photoisomerization of nitrostilbenes. 79
Photodissociation.-Photodissociation processes have continued to attract a great
deal of attention from both theoreticians and experimentalists. Two valuable
reviews of recent work on the photodissociation dynamics of polyatomic molecules
have been published 792, 793 and the new experimental techniques used in these
studies A theoretical representation of total photodissociation cross-
sections has been given which highlights the importance of short-time dynamics in
direct p h o t o f r a g m e n t a t i ~ nThe
. ~ ~ ~leading term of the resulting formula is a
classical cross-section. The subsequent terms are an expansion in the powers of h
and are quantum corrections to the classical term. An expression for the Doppler
spectrum of the electronically excited product species produced by a photodissoci-
ation process in a dilute gas has been derived using kinetic theory.796
785
G. Olbrich, Chem. Phys., 1978, 27, 117.
786
I . Beraldi, M. C. Bruni, F. Momicchioli. J . Langlet, and J . P. Malreii, Chem. Phys. Lett., 1977,51,493.
787
P. Tavan and K. Schulten, Chem. Phys. Lett., 1978, 56, 200.
S. Boue, D . Rondalez, and P. Vanderlinden, Jerusalem Symp. Quantum Chem. Biochem., 1977,10,199.
789 D. Huppert, P. M. Rentzepis, and D. S. Kilger, Phorochem. Phorobiol., 1977, 25, 193.
790 0. Teschke, E. P. Ippen, and G. R. Holten, Chem. Phys. Letr., 1977, 52, 233.
79'
H. Goerner and D. Schulte-Frohlinde, J. Phys. Chem., 1978, 82, 2653.
792
W. M. Gelbart, Annu. Rev. Phys. Chem.. 1977, 28, 323.
793 J. P. Simons, Gas Kinet. Energy Transfer, 1977, 2 , 58.
794 J . P. Simons, N B S Spec. Publ. (US), 1978, 526, 145.
795
E. J . Heller, J . Chem. Phys., 1978, 68, 2066.
796
M. S. Jhon and J. S. Dahler, J . Chem. Phys., 1978, 69, 819.
118 Photochemistry
The photodissociation cross-section of a diatomic molecule, represented by a
Poeschl-Teller oscillator model, has been calculate for the case where a single
absorbed quantum is sufficiently energetic to reach a dissociative state of the
Using HCl as a model it was shown that for lower vibrational states
the photodissociation cross-section was very small, whereas for higher vibrational
levels it becomes a dominating process. Calculations of the photodissociation cross-
sections for the sodium dimer cation Na,' 798 and the hydrogen deuteride cation
H D + 799 have been published. A moment analysis of the dynamics of the
photodissociation of linear triatomic molecules has shown a good agreement
between classical and quanta1 moments,800and the lineshape and final probability
distribution of such molecules undergoing photodissociation have been treated
using coupled equations.801An interesting paper has shown that disagreements in
the predicted isotope effects and role of interfragment repulsions in the photo-
dissociation of the HCN molecule can be traced to the lack of knowledge of any of
the details of the unbound potential-energy surface.802 The same authors have
published a comparison of Franck-Condon transition amplitudes for molecular
dissociation calculated using an exact quantum treatment.803 Large isotope effects
in the direct photodissociation of vibrationally excited molecules have been found
in calculations on model linear HCN and DCN molecules,804and a new approach
to the treatment of photofragmentation has been proposed which avoids the
difficulties normally associated with the calculation of Franck-Condon processes
by including time dependence explicitly.805A model for the photodissociation of
water has been developed and used to calculate the vibrational distribution ' 0 6 and
rotational angular momentum distribution 807 of the hydroxyl radical, OH ( A 2C+),
fragment. SCF-CI calculations of the low-lying singlet and triplet states of
hypochlorous acid, HOCl, have been published in a theoretical study of the U.V.
photodissociation of this molecule which could act as a stratospheric reservoir of
CL808The molecules' absorption spectrum is predicted to exhibit a single peak at
',
220 nm with an extinction coefficient of 123 1 mol- cm- and photodissociation of
the molecule is predicted to lead the C1 and OH as fragments. Calculations on the
photodissociation of formaldehyde have suggested that the barrier to products lies
above the first few vibrational levels of S , and therefore that collision-induced
effects must have been present in the results of recent experimental work.809The
various photodissociation reactions of ammonia have been investigated in SCF
calculations,8 l o and an analysis of the distribution of vibrationally excited states in
BCl,, whose v3 mode is resonant with the output of a CO, laser, has shown that the
'97
V. K. Khersonskii, Opt. Spektrosk., 1977, 43, 39.
798
M. Tadjeddine and G . Parlant, Mol. Phys., 1977, 33, 1797.
799
T. Uzer and A . Dalgarno, Chem. Phys. Lett., 1979, 61, 213.
0. Atabek and R. Lefebvre, Chem. Phys. Lett., 1977, 52, 29.
0. Atabek and R . Lefebvre, J . Chem. Phys., 1977,67,4983.
M . D . Morse, K. F. Freed, and Y. B. Band, Chem. Phys. Lett., 1977,49, 399.
Y . B. Band, M. D . Morse, and K . F. Freed, J . Chem. Phys., 1978,68, 2702.
J. A. Beswick, M. Shapiro, and R. Sharon, J . Chem. Phys., 1977, 67, 4045.
K. C. Kulander and E. J. Heller, J . Chem. Phys., 1979, 69, 2439.
R. Akamatsu and K . Oohata, J . Phys. SOC.Jpn., 1977, 43, 264.
R. Akamatsu and K . Oohata, J . Phys. SOC.Jpn., 1978, 44, 589.
R. L. Jaffe and S. R. Langhoff, J . Chem. Phys., 1978,68, 1638.
D. F. Heller, M. L. Elert, and W. M . Gelbart, J . Chem. Phys., 1978,69,4061.
R. Runau, S. D. Peyerimhoff, and R. J . Buenker, J . Mof. Spectrosc., 1977, 68, 253.
rate of photodissociation can be dramatically increased by an appropriate detuning
of the light.8 l 1
An interesting computer simulation of the cage effect has been able to reproduce
features of experimental investigations of this effect.' The simulation computed
the classical trajectories of a system comprising I, and 22 inert-gas atoms confined
in a spherical volume. The cage effect in rare-gas solid matrices has been used to
study the predissociation of ICl and the direct dissociation of C1, and MeI,'13 and,
to come full circle, it may be mentioned that liquid-crystalline solvents can greatly
enhance the photodimerization rate of a molecule such as acenaphthylene.814
Magnetic-field Effects.-Following a period of rapid growth in interest in magnetic-
field effects, which was reported on in the last appearance of this chapter and during
which a number of important new observations were published, there has been a
period of steadier progress. The study of the geminate recombination of radical ions
in the radiolysis of hydrocarbons, using magnetic-field effects, has been dis-
cussed,815and the results of a study of the magnetic-field effect on the recombi-
nation fluorescence from pulsed and continuously irradiated solutions of anthra-
cene in hydrocarbon solvents were found to be in general agreement with a recent
theory of such effects.' l6 In the latter study the fluorescence intensity was found to
increase with the magnetic-field strength, and the enhancement was found to be
greater in squalane as a solvent than in cyclohexane where the enhancement was
greater than that in benzene as a solvent. Earlier studies of the magnetic-field
dependence of the triplet yield that results following a photoinduced electron-
transfer process in the system pyrene-3,5-dimethoxy-NN-dimethylaniline in
methanol have been extended to include the effects of changes in the solvent polarity
and of using perdeuteriated solute molecules.' l 7 The results from these systems and
those from studies of the bacterial photosynthetic reaction centre have been
discussed elsewhere.*l 8 The isotope effect has also been investigated for the
photochemically generated PhN' Et,'- anthracenide radical anion exciplex ion
pair which forms a free-radical ion with magnetic-field-dependent yield. l 9 A laser
double-pulse technique for the study of the time-dependent behaviour of free
radicals by exciting their fluorescence has been described 8 2 0 and used in studies of
magnetic-field effects on the recombination of radical pairs and on the electronic-
energy transfer from triplet benzophenone to the ketyl radical 8 2 1 processes which
occur on photolysis of benzophenone.
Studies of the effect of magnetic fields on the product yields of chemical reactions
have met with mixed success. A study of the product yields in the photolysis of
CBrCl, in the presence of PhMe has shown that the effect of a 1.25 T magnetic field
'I2
J . N . Murrell, A, J. Stace, and R. Dammel, J . Chem. SOC.,Faraduy Trans. 2, 1978, 74, 1532.
'I3
L. E. Brus and V. E. Bondybey, NBS Spec. Publ. ( U S ) , 1978, 526, 251.
' I L J. M. Nerbonne and R . G. Weiss, J . Am. Chem. Soc., 1979, 101, 402.
'I5
B. Brocklehurst, Nature (London), 1977, 265, 613.
'I6
R . S. Dixon, F. P. Sargent, V. J. Lopata, E. M. Gardy, and B. Brocklehurst, Can. J . Chem.. 1977,55,
2093.
'I7
H. J . Werner, H. Staerk, and A. Weller, J . Chem. Phys., 1978, 68, 2419.
"' K. Schulten and A. Weller, Biophys. J . , 1978, 24, 295.
'" W. Bube, R. Haberkorn, and M . E. Michel-Beyerle, J . Am. Chem. Soc., 1978, 100, 5993.
"O
H. Staerk and K. R . Naqvi, Chem. Phys. Lett., 1977, 50, 386,
"' K . R. Naqvi, H. Staerk, and T. Gillbro, Chem. Phys. Lett.. 1977, 49, 160.
120 Photochemistry
was less than 2% and as such is smaller than that predicted theoretically.822 In
contrast, a study of the photolysis of dibenzyl ketone in a soap solution resulted in a
’
field-dependent 3C-isotopeenrichment at the carbonyl C atom of the unconverted
ketone of, remarkably, approaching l O O Y O .Magnetic-field
~~~ effects have been
observed in the photolysis of isoquinoline N-oxide 8 2 4 and serum albumin . 8 2 5 It
has been pointed out that the theory of the magnetic-field dependence of delayed
fluorescence from solutions of aromatic hydrocarbons predicts a crossover at a
particular field strength H , in the ratio of the relative polarized fluorescence
intensities.826It is expected that for fields of H < H , the parallel polarized branch
will be above the perpendicularly polarized branch. For fields H > H , this order is
reversed. It has been noticed that the intensity of delayed fluorescence from crystals
of pyrene and 4,5-methylenephenanthrene(oriented in a particular direction with
respect to the field) changed when the direction of an applied steady magnetic field
was reversed,82 and magnetic-field studies have proved valuable in elucidating the
mechanism of excimer formation in triplet-triplet annihilation reactions of
solutions of aromatic molecules.828
There have been several studies of the influence of magnetic fields on reactions in
photosynthetic bacteria, principally Rhodopseudornonas sphaeroides (R.s.). A
magnetic-field dependence of the yield of triplet products generated in the reaction
centres of R.s. has been observed, and the results have been discussed in terms of a
model involving the primary electron-transfer process.829The model predicts that
there should be a temperature dependence of the magnetic-field behaviour of the
triplet yield and that there will be a magnetic-field effect on fluorescence quantum
yield of the reaction centre. Such effects on the fluorescence have been observed in
two investigations of R . S . ~ ~
8 3’1 ?but with marked differences in magnitude.
There have been further reports of the magnetic quenching of the fluorescence of
molecules in the gas phase. A study of the pressure dependence of the fluorescence
quenching of gaseous glyoxal has revealed two regions of behaviour of the collision-
free lifetime on the magnetic-field strength.832For fields above 5 k G it took a
constant value greater than the no-field value, and for fields below 5 kG it was a
function of the field strength. The results were explained in terms of a direct
mechanism in which the field introduced a Zeeman term to the interaction. A
parallel study of protonated and deuteriated glyoxal by a different research group
reached different conclusions regarding the collision-free lifetimes.8 3 3 They found
them to be unaffected by the presence of the field. There has been a useful discussion
of the magnetic quenching of luminescence in relation to the electronic structure of
E. J . Broomhead and K . A. McLauchlan, J . Chem. Soc.. Faraday Trans. 2, 1978, 74, 775.
N . J . Turro and B. Kraeutler, J . Am. Chem. Soc., 1978, 100, 7432.
N . Hata, Chem. Lett.. 1978, 1359.
0 . G. Kadnikov and V. I . Kobizskoi, Pis’ma Zh. Tekh. Fiz., 1978, 4, 1367.
K . Lendi, Chem. Phys. Lett.. 1977, 50, 485.
”’
82b
R . C. Johnson, Chem. Phys. Lett., 1977, 49, 85.
K . R . Naqvi, H. Van Willigen, and D. A. Capitanio, Chem. Phys. Lett., 1978, 57, 197.
829 H. J . Werner, K . Schulten, and A. Weller, Biochim. Biophys. Acta. 1978, 502, 255.
830 H. G. De Vries and A. J. Hoff, Chem. Phys. Lett., 1978, 55, 395.
83’ V. M. Voznyak, E. I. Elfinov, and I. I . Proskuryakov, Dokl. Akad. Nauk SSSR, 1978, 242, 1200.
A. Matsuzaki and S. Nagakura, Helv. Chim. Acta. 1978, 61, 675.
833 ( a ) H. G . Kuettner, H. L. Selzle, and E. W. Schlag, fsr. J . Chem., 1977,16,264; ( b ) Chem. Phys. Lett.,
1977,48, 207; ( c ) Chem. Phys., 1978, 28, 1 .
molecules.834 The effect is expected to be weak for aromatic hydrocarbons but
strong for molecules where the singlet and triplet states have n-n* character and are
mixed by a spin-orbit interaction. Unfortunately lack of space has prevented any
reportage of Zeeman- and Hanle-effect studies.
Chemically Induced Dynamic Magnetic Polarization.-The techniques of chemi-
cally induced dynamic electron (nuclear) polarization, CIDE(N)P, are now well
established, and the papers reported on here have been selected for their general
interest. A perturbational treatment of radical-pair theory has been used as a basis
for the discussion of the field dependence of the CIDNP effect at low fields
( < 1 kG),835and the same author has suggested the use of a new exit-channel
parameter to remove an ambiguity in the interpretation of CIDNP spectra when the
radical pair leads to the triplet state of the reaction
There have been several interesting applications of CIDNP to systems of
biological interest. Recent studies have shown that photo-CIDNP can be of use in
determining structural information in native proteins. A study of porcine
pancreatic phospholipase A, and its precursor found nuclear spin polarization
signals from the tryptophan-3 and tyrosine-69 and -123 residues, the first two of
which are located in the phospholipid binding site.837In a related study the CIDNP
spectra of the simple aromatic amino-acids were first established to help interpret
the results of photo-CIDNP studies on bovine pancreatic trypsin inhibitor, RNase
A, RNase S, and l y s ~ z y m eA. ~particularly
~~ interesting study of bovine pancreatic
trypsin inhibitor has been published in which a laser was used to excite a dye, 3-N-
carboxymethyl lumiflavin, in a dye-protein solution.839Photo-CIDNP signals were
observed which were attributable to two surface tyrosine residues, -10 and -21.
CIDMP measurements in biological systems have been discussed in a brief
review.840
CIDNP effects have been able to distinguish two mechanisms in the electron-
transfer-photosensitized isomerization of styrene derivatives.841 Donor styrenes
were found to rearrange in the radical cation whereas acceptor styrenes rearrange in
a non-planar triplet state. A CIDNP study has proved valuable in studying the
initial stages of a photoinduced polymerization reaction in which the photoinitiator
was an a l k o x y a ~ e t o p h e n o n eand
, ~ ~an
~ acid-base equilibrium has been observed in
the photo-CIDNP of nitroaromatic compounds.843 The photoreductions of
benzophenone by thio ethers,844uethyl s ~ l p h i d eand , ~ ~secondary
~~ alcohols 845
have all been investigated by CIDNP. A study of the electron-transfer quenching of
photoexcited aryl alkyl ketones has revealed the presence of concentration- and
B. F. Minaev, Opt. Spektrosk., 1978, 44, 256.

835 G. L. Closs, NATO Adv. Study Inst. Ser., Ser. C. 1977, 34, 225.
G . L. Closs and M. S. Czeropski, J. Am. Chem. SOC.,1977, 99, 6127.
837 E. H. J . M. Jansen, H. Meyer, G . H. De Haas, and R. Kaptein, J. Biol. Chem., 1978, 253, 6346.
R38 R. Kaptein, Jerusalem Symp. Quanrum Chem. Biochem., 1978, 1 1 , 211.
839 R. Kaptein, K . Dijkstra, and K . Nicolay, Nature (London), 1978, 274, 293.
840 G . L. Closs, NATO Adv. Study Inst. Ser., Ser. C, 1977, 34, 357.
841 H . D . Roth and M. L. M. Schilling, J . Am. Chem. SOC., 1979, 101, 1898.
842 A. Borer, R. Kirchmayr, and G. Rist, Helv. Chim. Acta, 1978, 61, 305.
843 K . A. Muszkat, Chem. Phys. Lett., 1977, 49, 583.
844 ( a ) G. Vermeersch, J . Marko, N. F. Garot, S. Caplain, A. Couture, and A. Lablache-Combier,
Tetrahedron, 1978, 34, 2453; ( 6 ) Tetrahedron Lett., 1977, 829.
845 J . A. Den Hollander, A. J . Hartel, and P. H. Shippers, Tetrahedron, 1977, 33, 21 1.
122 Photochemistry
’
acidity-dependent 9F CIDNP signals, which can be explained using both the
radical-pair and the triplet mechanisms. 846 An anomalous CIDNP enhancement at
low fields has been observed in the photolysis of c y c l o d ~ d e c a n o n e . ~ ~ ~
A new technique which combines flash photolysis with a pulsed magnet capable
of producing inductions of 200kG has been used to study the reaction of the
nitrogen trioxide radical with Ce”’ in acidic aqueous solution at 25°C.848 The
authors argue that the technique is a new way of studying CIDEP effects that is
independent of magnetic resonance. The results of photo-CIDEP studies on aspects
of photosynthesis have been reviewed,849 and a recent study of green plant and
algal species has detected CIDEP signals which apparently arise from photosystem
I and involve a radical-pair CIDEP studies of the photoreduction of
(MeCO), by Et,N,851 the photoreduction of t-b~tyl-p-benzoquinones,~~~ and the
relative importance of hydrogen abstraction and electron transfer in the photo-
reduction of 1,4-naphthoquinone s , have been published.
Proton Transfer.-The excited-state proton-transfer reactions of aromatic mole-
cules have been reviewed (in Russian),854and the fundamental aspects of the
acid-base chemistry of electronically excited organic molecules in solution and its
effect on their fluorescence properties have also been discussed.855The determi-
nation of the acidity constants in the first excited states of molecules and the
existence of linear free-energy relationships have been discussed with reference to
anilines and benzoic and linear relations between the ground and first
excited singlet state basicities, pK and p P respectively, of flavones and benzazoles
have been found.857An expression has been derived from a steady-state kinetic
treatment of a general excited-state reversible reaction which linearly relates the
total luminescence and the concentration of one of the reactants.858 Using a
method based on this result, which does not involve the separation of the total
fluorescence into its components, the author obtained values of the first excited
singlet state acidity constants of acridone, xanthone, and thioxanthanone in I : 1
H,O-EtOH as a solvent, which agreed with previous determinations using other
approaches.
Of the numerous experimental investigations of excited-state proton-transfer
reactions mention is made of a few which are of general interest. An important
result with respect to the fluorescence properties of proteins is the observation of the
fluorescence of the tyrosinate ion in concentrated buffer solutions at neutral pH.859
H46 M. L. M. Schilling, R. S. Hutton, and H . D . Roth, J . Am. Chem. SOC.,1977, 99, 7792.
84’ A. V . Dushkin, Yu. A . Grishin, and R. Z . Sagdeev, Chem. Phys. Lett., 1978, 55, 174.
848 T. W. Martin and M . V. Stevens, NBS Spec. Puhl. (US), 1978, 526, 126.
84y A. J. Hoff and H . Rademaker, NATO Adv. Study Inst. Ser.. Ser. C , 1977, 34, 399.
850 A . R. McIntosh, H. Manikowski, S. K. Wong, C. P. S. Taylor, and J. R. Bolton, Biochem. Biophys.
Res. Commun., 1979, 87, 605.
”’ K . A . McLauchlan, R. C. Sealy, and J . M . Wittmann, J . Chem. SOC.,Faraduy Trans. 2, 1977,73,926.
H5L T. Foster, A. J . Elliot, B. B. Adeleke, and J . K . S. Wan, Can. J. Chem.. 1978, 56, 869.
H53 S. K . Wong, J . Am. Chem. Soc., 1978, 100, 5488.
8s4 I. Yu. Martynov, A . B. Demyashkevich, B. M. Uzhinov, and M. G. Kus’min, Usp. Khim.,1977,46,3.
855 S. G. Schulman in ‘Modern Fluorescence Spectroscopy’, ed. E. L. Wehry, Plenum, New York, 1976,
Vol. 2, p. 239.
Hs6 D . Sengupta and S. C. Lahiri, Z . Phys. Chem. (Leipzig), 1977, 258, 1097.
857 Yu. L. Frolov, Yu. M. Sapozhnikov, N . N . Chipanina, V. F. Sidorkin, and N . A . Tyukavkina, Izv.
Akad. Nauk S S S R , Ser. Khim., 1978, 301.
F. Celardin, Z . Phys. Chem. (Wiesbaden), 1977, 106, 25.
”’ D. M. Rayner, D . T. Krajearski, and A. G . Szabo, Can. J. Chem.. 1978. 56, 1238.
Previously this fluorescence had only been observed at p H > pK ( S o ) = 10.3,
where the tyrosinate form exists in the ground state. The result confirms the large
shift of pK(S,) with respect to pK(S,) and the proton-transfer mechanism of the
carboxylate ion quenching of tyrosine fluorescence. An investigation of the excited
singlet state proton transfer of 1- and 2-naphthol and 1-azaphenanthrene by nano-
second-pulse fluorometry, which uses a new method of numerical data treatment,
has failed to find any evidence of a proton-transfer reaction from an unrelaxed
state.860The picosecond formation kinetics of the phenolate anion of 4-methyl
umbelliferone in neutral solution and its tautomer in acidic solutions have been
observed directly,861 and the establishment of a prototropic equilibrium for the
lowest excited singlet state of 2-naphthol-6,8-disulphonate has been demonstrated to
hold over most of the inflection region in the fluorimetric titration.862 An
investigation of the intramolecular proton transfer in the excited state of 6-(2-
hydroxy-5-methylphenyl)-s-triazines,using picosecond time-resolved spectros-
copy, found that there was no isotope effect on the transfer rate constant.863This is
evidence against a tunnelling mechanism being involved. The excited-state proton
association of acridine to give the acridinium ion has been found to be dependent on
the wavelength of excitation,864 and the excited-state proton transfer of p-
aminosalicylic acid has been shown to occur in the solid state as well as in
solution . 8 6
"""' A. B. Demyashkevich, N. K. Zaitsev, and M. G. Kus'min, Chem. Phys. Lett., 1978, 55, 80.
Kobayashi, J . Phys. Chem., 1978, 82, 2277.
'" T.S. G. Schulman, L. S. Rosenberg, and W. R. Vincent,jun., J . Am. Chem. SOC.,1979, 101, 139.
8b3
H. Shizuka, K. Matsui, Y.Hirata, and I . Tanaka, J . Phys. Chem., 1977, 81, 2243.
864
P. Gangola, N. B. Joshi, and D. D. Pant, Chem. Phys. Lett., 1979, 60,329.
S. E. Morsi and J . 0. Williams, J . Chem. SOC.,Perkin Trans. 2, 1978, 1280.

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Spectroscopic and Theoretical Aspects

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1

Spectroscopic and Theoretical Aspects

2 Calculations of Electronically Excited States

coefficients obtained from variational equations, S,+ the symmetry-adapted

The local approach for the calculation of electronic correlation energies in

*O P. Horsch, 2. Phys. B, 1979, 33, 43.

'' P. Politzer, J . Chem. Phys., 1978, 69, 491.

to estimate non-adiabatic effects in the photodissociation of the molecular B'q,

41 E. A. Gordeev, E. E. Nikitin, and A. I. Shushin, Mol. Phys., 1977, 33, 161 1.

As a test of the applicability of pseudopotential techniques to calculations of

45 P. F. Zittel, G. B. Ellison, S. V. O'Neill, E. Herbst, W. C. Lineberger, and W. P. Reinhardt, J . Am.

56 S. R. Langhoff and J. 0. Arnold, J . Chem. Phys., 1979, 70, 852.

Figure 4 Correlation diagram of the states of 0 , at the ground-state geometry (verticfe)and

'* G. V . Shlyapnikov and I . P. Shmatov, 0 p 1 . Spektrosk., 1978, 45, 487.

S. Iwata and K. Morokuma, Theor. Chim. Acta, 1977, 44, 323.

appeared. 98 Extended Huckel calculations have been used to develop a theoretical

availability of experimental data and results from a number of previous high-

V. I. Danilov and N. V. Zheltovsku, Mol. Genet. Giofiz., 1976, I , 10.

Table l a Excited states of the reduced model Fe(SH),*- (energies in eV)

integral equation, which with an appropriate boundary condition is called the

14’ R . G. Woolley, Chem. Phys. Lett., 1978, 55, 443.

solvent, q is electrostatic charge, and y is a Coulomb integral, to calculate values of

pressure, w2 is the force constant, Q a configuration co-ordinate, c a coupling

155 R. C. Tompkins, J . Chem. Phys., 1978, 69, 579.

I) +cT Charge transfer

LUMO and the lower is the HOMO

result supports earlier work on the multiple fluorescences of (1) observed in

Table 2b Triplet energy levels (ETI)

of copper and metal-free phthalocyanines have been characterized in a laser

small to detect. A theoretical treatment of two-photon excited fluorescence(TPEF)

A new quantum statistical theory of optical phenomena, which uses a density-

’I8 M. C. Li, Nuovo Cimento SOC.Ital. Fis. B, 1977, 39, 165.

225 B. Cagnac, A t . Phys.. 1977, 5 , 147.

248 J. P. Woerdman, Chem. Phys. Lett., 1977, 50, 41.

dichroism, and other optical properties, in a force-free rotational diffusion process

2H3 J. Sagiv, Tetrahedron, 1977, 33, 2315.

have been interesting reports of the asymmetric synthesis of N-methyl-

302 I . Tinoco, jun., Electro-Opt. Ser., 1976, 1, 367.

Chromophore Posit ion +I -I +I? -I? Example

N 0 0 -0, then - -0, then +

k,,, = dh2C X (cth+phwj + u)JjEjuc2

4 Intramolecular Excited-state Decay Processes

3s0 Y. Prior and J . A. Kash, Phys. Rev. A , 1978, 18, 2603.

3 s 2 F. Fischer, Phys. Status Solidi A , 1979, 52, 189.

[ = JdEplE)exp( - BE)] is the partition function. This expression can be developed

to obtain the quantum-mechanical equivalents to the rate constants of a simple

Inver se Etec t ronic Relaxation

Radiative I nt ram ole c ula r

358 V. Seshadri and V. M . Kenkre, Phys. Rev. A , 1978, 17, 223.

Theories of Radiationless Decay Processes.-A major experimental and theoretical

Figure 17 Various routes to approach the exact non-adiabatic wavefunction

measurements of naphthalene fluorescence in the collision-free low-pressure region

400 s. Kobayashi, K. Kikuchi, and H. Kokubun, Chem. Phys., 1978,27, 399.

been studied by a flash-photolysis technique.409 The general dependence was in

dependent on solvent polarity and where ct denotes a charge-transfer emission

42h S. Okajima and E. C. Lim, J . Chem. Phys.. 1978, 69, 1929.

435 D. A. Chernoff and S. A. Rice, J . Chem. Phys., 1979, 70, 2521.

interaction with a driving field and an incoherent interaction with a thermal

with the figure of 450 f 55 ps obtained using picosecond pulsed-laser techniques.

Homogeneous I inewidth Ir,)of A p i b r o n i c lines

489 P. Kusch and M . M. Hessel, J . Chem. Phys., 1978, 68, 2591.

Figure 23 Energy diagram illustrating the dependence of the Sn,l + So Juorescence

A vibrational analysis of the S, + S , fluorescence of azulene in a naphthalene

525 N. J . Bunce, Chem. Phys. Lett., 1978, 59, 66.