J. Phys. Chem.

1991, 95, 7973-7993 7973

Femtosecond Real-Time Probing of Reactions. 7. A Quantum and Classical

Mechanical Study of the ICN Dissociation Experiment

Gareth Roberts and Ahmed H. Zewail*

Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology,
Pasadena, California 91125 (Received: March 21, 1991)

A comparison is presented between experiment and quantum and classical simulations of the time-dependent dynamics of
the dissociation reaction of ICN via the A continuum. To illustrate the approach, second-order perturbation theory and
a classical model (Ber. Bunsen-Ges. Phys. Chem. 1988, 92, 373) are employed to calculate the real-time behavior of dissociating
[I—CN]** species during the course of the reaction. In this way, the abilities of the two methods to describe accurately
the reaction dynamics as revealed experimentally are evaluated: it is found that both quantum dynamical and classical mechanical
treatments are capable of reproducing the essential temporal features probed by experiment and that, in this instance, classical
equations of motion offer an adequate description of the process of nuclear separation. The difference between the relevant
excited-state potential functions (over the long-range region) employed in the calculations is recovered from the simulated
data by means of an inversion procedure (J. Chem. Phys. 1989, 90, 829) that relates absorption of the probing laser pulse
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to interfragment distance along the reaction coordinate. In addition, the variation in calculated transient behavior resulting
from changes in the parameters describing the functional forms of the two potentials governing the observed reaction dynamics
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is examined in terms of their effect on characteristic reaction dissociation times, the lifetimes of transition-state configurations,
and inversion to the difference between potential energy curves. Finally, comparison is made with analogous experimental
and theoretical investigations of the fragmentation of the heavier Bi2 molecule.

I. Introduction increase in laser induced fluorescence (LIF) signal intensity to

The dissociation of cyanogen iodide was one of the first gas- some final asymptotic value attained at r =* 500 fs. From these
phase reactions to be studied1'7 in real time in the femtosecond (1) Scherer, N. F.; Knee, J. L. Smith, D. D.; Zewail, A. H. J. Phys. Chem.
regime.8'11 This reaction has received considerable attention 1985, 89, 5142.
throughout the last twenty or more years, having been the object (2) Dantus, M.; Rosker, M. J.; Zewail, A. H. J. Chem. Phys. 1987, 57,
of detailed investigation by means of a broad range of experi- 2395.
mental12'32 and theoretical33""66 techniques. It is now well estab- (3) Rosker, M. J.; Dantus, M.; Zewail, A. H. Science 1988, 241, 1200.
(4) Rosker, M. J.; Dantus, M.; Zewail, A. H. J. Chem. Phys. 1988, 89,
lished12'13·19·21"25 that following electronic excitation via the A 6113.
continuum, ICN dissociates through two exit channels, leading (5) Dantus, M.; Rosker, M. J.; Zewail, A. H. J. Chem. Phys. 1988, 59,
to ground-state and spin-orbit-excited iodine atoms respectively: 6128.
(6) Dantus, M.; Bowman, R. M.; Baskin, J. S.; Zewail, A. H. Chem. Phys.
Lett. 1989, 159, 406.
ICN + hv (210 < < 350 nm) —
[I-CN]** —
(7) Zewail, A. H. J. Chem. Soc., Faraday Trans. 2 1989, 85, 1221.
(8) Zewail, A. H. Science 1988, 242, 1645.
l(2P3/2) + CN(X2Z+) (la) (9) Zewail, A. H.; Bernstein, R. B. Chem. Eng. News 1988, 66 (Nov 7),
24.
[I-CN]*· (10) Gruebele, M.; Zewail, A. H. Phys. Today 1990, 43 (5), 24; Ber.
l(2P1/2) + CN(X22+) (lb)
— —

Bunsen-Ges. Phys. Chem. 1990, 94, 1210.

Time-integrated studies of the dissociation have provided many
detailed features of the dynamics of both exit channels, (la) and
(lb). Such an approach has involved a variety of methods, in-
cluding measurements of photofragment polarization and time-
of-flight distributions,12 product quantum-state-resolved distri-
butions,13"20 sub-Doppler laser-induced fluorescence,21·22 absolute
quantum yields of I(2Pw2) atoms,22"25·29·31 and the spatial an-
isotropy and relative alignment of the separating photopro-
ducts.21,22,26"32
Real-time investigations of reaction 1 have utilized the technique
of femtosecond transition-state spectroscopy (FTS),5·8"10 by which
[I—CN]** transition-state configurations in the process of sepa-
rating to form I(2P3/2,i/2) + € ( 2 +) products have been
monitored as a function of time.1"6 The pump-laser pulse initiates
reaction within the long-wavelength tail of the A continuum at
=
306 and 285 nm: most experiments have employed a
pump-laser wavelength of = 306 nm,1"3,5·6 however, and have
thus been directed toward probing reaction la in which only
ground-state iodine atoms are energetically feasible. When the
probe laser is tuned to = 388.5 nm, commensurate with the band
head of the P branch of the well-known CN(B22+ ·«— 2 + (0,0))
band system,14·15·67"70 an induction period lasting about 200 fs after
time zero (pump excitation) is observed2"6 followed by a monotonic
Contribution 8409 of the Arthur Amos Noyes Laboratory of Chemical
Physics. The investigations reported in this paper were begun while Professor
R. B. Bernstein was a Sherman Fairchild Distinguished Scholar at Caltech:
we have benefited greatly from his contribution to the initial stages of this
work and from many hours of stimulating discussions.
(11) Khundkar, L. R.; Zewail, A. H. Ann. Rev. Phys. Chem. 1990, 41, 15.
(12) Ling, J. H.; Wilson, K. R. J. Chem. Phys. 1975, 63, 101.
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C. H. Chem. Phys. 1983, 82, 443.
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Sadowski, C. M. Chem. Phys. 1984, 89, 457.
(19) Marinelli, W. J.; Sivakumar, N.; Houston, P. L. J. Phys. Chem. 1984,
88, 6685.
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2120.
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Discuss. Chem. Soc. 1986, 82, 79.
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0022-3654/91 /2095-7973S02.50/0 &copy; 1991 American Chemical Society

7974 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991
data the time taken for the CN radical to separate from the force
field of the iodine atom (so as to be spectroscopically identifiable
in its final internal quantum-state distribution) has been measured
as T|/2 = 205 ± 30 fs for this pump wavelength.3,5 By detuning
the probe laser to wavelengths to the red of the 2 + — 2 +
band, a rise and decay in the LIF signal is monitored, from which
it has been determined that [I—CN]4* transition states persist
for times of the order of 20-50 fs.4,5 From data of these types,
various radial characteristics of the potential energy surface (PES)
controlling dissociation have been deduced.5,62,63
Experiments that involve detuning the probe laser to the blue
of the = 388.5 nm line permit the formation of CN in different
rotational levels to be examined, a corresponding increase in r,»
being monitored with increasing product rotational excitation.5,7
These results have been discussed in terms of the time development
of angular momentum during the dissociation reaction, leading
to an asymptotic (long-time) distribution of rotational states of
CN final product;7 the observed variation of n is too small to
be simply explained by a decrease in the available translational
energy with increasing product rotation but rather reflects the
degree of torque acting on bent50,56,57 ICN in the excited A state
and the angular topology (and centrifugal effects) of the disso-
ciative PES. By advantageous use of the inherent polarization
properties of the laser pulses, the time dependence of coherence
and alignment in reaction 1 have also been investigated6 and the
observations related to the angular part of the excited-state PES.7
(35) Morse, M. D.; Freed, K. F.; Band, Y. B. Chem. Phys. Lett. 1976,44,
125.
(36) Halavee, U.; Shapiro, M. Chem. Phys. 1977, 21, 105.
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3604, 3620.
(39) Beswick, J. A.; Gelbart, W. M. J. Phys. Chem. 1980, 84, 3148.
(40) Morse, M. D.; Freed, K. F. J. Chem. Phys. 1981, 74, 4395.
(41) Heather, R. W.; Light, J. C. J. Chem. Phys. 1983, 78, 5513.
(42) Williams, S. O.; Imre, D. G. J. Phys. Chem. 1988, 92, 6636, 6648.
(43) Heather, R.; Metiu, H. Chem. Phys. Lett. 1989, 157, 505.
(44) Lee, S.-Y.; Pollard, W. T.; Mathies, R. A. Chem. Phys. Lett. 1989,
160, 531.
(45) Henriksen, N. E.; Heller, E. J. J. Chem. Phys. 1989, 91, 4700.
(46) Jacon, M.; Atabeek, O.; Leforestier, C. J. Chem. Phys. 1989, 91,
1585.
(47) ViguS, J.; Girard, B.; Gouédard, G.; Billy, N. Phys. Rev. Lett. 1989,
62, 1358.
(48) Guo, H.; Schatz, G. C. J. Chem. Phys. 1990, 92, 1634.
(49) Beswick, J. A.; Jortner, J. Chem. Phys. Lett. 1990, 168, 246.
(50) Yabushita, S.; Morokuma, K. Chem. Phys. Lett. 1990, 175, 518.
(51) Krause, J. L.; Shapiro, M.; Bersohn, R. J. Chem. Phys., submitted
for publication.
(52) Pattengill, M. D. Chem. Phys. 1983, 78, 229.
(53) Pattengill, M. D. Chem. Phys. 1984, 87, 419.
(54) Waite, B. A.; Helvajian, H.; Dunlap, B. L; Baronavski, A. P. Chem.
Phys. Lett. 1984, 111, 544.
(55) Goldfield, E. M.; Houston, P. L.; Ezra, G. S. J. Chem. Phys. 1986,
84, 3120.
(56) Dugan, C. H.; Anthony, D. J. Phys. Chem. 1987, 91, 3929.
(57) Dugan, C. H. J. Phys. Chem. 1988, 92, 720.
(58) Benjamin, I.; Wilson, K. R. J. Chem. Phys. 1989, 90, 4176.
(59) Yan, Y. J.; Fried, L. E.; Mukamel, S. J, Phys. Chem. 1989,93, 8149.
(60) Mukamel, S. Ann. Rev. Phys. Chem. 1990, 41, 647.
(61) Fried, L. E.; Mukamel, S. J. Chem. Phys. 1990, 93, 3063.
(62) Bersohn, R.; Zewail, A. H. Ber. Bunsen-Ges. Phys. Ckem. 1988, 92,
373.
(63) Bernstein, R. B.; Zewail, A. H. J. Chem. Phys. 1989, 90, 829.
(64) Holdy, K. E.; Klotz, L. C.; Wilson, K. R. J. Chem. Phys. 1970, 52,
4588.
(65) Simons, J. P.; Tasker, P. W. Mol. Phys. 1973, 26, 1267.
(66) Brown, R. C; Heller, E. J. J. Chem. Phys. 1981, 75, 186.
(67) Jevons, W. Proc. R. Soc. A (London) 1926, 112, 407.
(68) Kiess, N. H.; Broida, . P. J. Mol. Spectrosc. 1961, 7, 194.
(69) Engleman, R., Jr. J. Mol. Spectrosc. 1974, 49, 106.
(70) Jackson, W. M. J. Chem. Phys. 1974, 61, 4177.
Roberts and Zewail
Theoretical studies of reaction 1 have also been numerous.33-66
Many (earlier) investigations have concentrated on the calculation
of absorption cross sections,37,45,48,64,66 product-state branching
ratios,48,55 frequency-resolved absorption, fluorescence, and Raman
spectra,36,38,45,46 and CN internal-state distribu-
tions33-36,38-41,45,46,48,52-56,64,65 from quantum mechanics33-51 and
by means of classical4-6,52-63 and semiclassical19,64-66 procedures.
More recently, the application of ultrafast laser methods to the
investigation of reaction 1 has prompted a range of calculations
to be carried out that aim to predict the observed real-time be-
havior from quantum42-44,51 or (semi)classical mechanics.58-63
Most such studies in this vein have adopted a time-dependent
approach,42-44,58-63 with a view to providing a rigorous conceptual
framework within which a quantitative understanding of the many
dynamical features of reaction 1 probed experimentally in the
time-domain may be obtained.
Bersohn and Zewail have offered a classical description of
reaction 1, in which the time dependence of absorption of the
probing laser pulse was related to an analytical form of a one-
dimensional repulsive PES for dissociation.62 The results of this
model reproduced the major features of the experimental FTS
observations.2,3,5 This work was extended by Bernstein and Ze-
wail,63 who outlined a classical method for inverting the data
obtained from FTS experiments to the difference between the
excited-state PESs connected by the probe laser. These authors
applied their procedure to reaction la, recovering an exponential
repulsive form of the parametrized potential energy curve over
which dissociation occurs when the upper PES accessed by the
probe laser is assumed to be constant over the range of inter-
fragment separations involved.63 In addition, consideration was
also given to the treatment of one-dimensional PESs that were
not purely repulsive functions of the reaction coordinate, for
example when one or both of the excited-state PESs possesses a
long-range van der Waals minimum.
Williams and Imre42 carried out the first time-dependent
quantum calculation of reaction la, computing the motion of wave
packets over a repulsive PES that involved a single radial coor-
dinate and obtaining FTS spectra in good qualitative agreement
with those determined experimentally.2,3,5 Heather and Metiu
have calculated time-dependent rotational coherence effects for
reaction la, employing a similar method by including the effect
of rotational motion of the CN photoproduct,43 which was pre-
viously treated by Zewail in terms of the time-evolution of CN
rotational alignment.7 A quantum dynamical approach has
likewise been employed by Lee et al. to calculate transient ab-
sorption cross-sections for ICN dissociation from the temporal
overlap of the two moving wave packets created by the pump- and
probe-laser pulses.44 Henriksen and Heller45 and Jacon et al.46
have applied a quantum-mechanical wave packet treatment to
derive Raman emission spectra and absorption cross sections for
dissociation of ICN.
From the time-evolution of classical trajectories over model
PESs, absorption spectra as a function of time for the dissociation
of ICN in both the gas phase and in Ar and Xe solvents have been
computed by Benjamin and Wilson,58 who obtained excellent
agreement with experimental results.2,3,5 Mukamel and co-workers
have examined the ICN dissociation reaction, using a correlation
function description of nonlinear optical processes in molecules
based on a quantum phase-space representation of the density
matrix,59,60 further extending their approach to derive classical
formulas for transition-state absorption of the probe-laser pulse.60,61
In this way, these authors were able to delineate in detail the
various criteria necessary for successful application of classical
models of molecular dissociation in the time domain in terms of
the different temporal regimes for nuclear separation, wave packet
dephasing, and laser pulse length.59-61 Density matrix methods
have also been utilized by other groups of workers to compute
femtosecond time- and frequency-resolved spectra of molecular
species in both the gaseous and solution phases.71-74 A theoretical
(71) Lin, S. H.; Fain, B. Chem. Phys. Lett. 1989, 155, 216.
(72) Fain, B.; Lin, S. H.; Hamer, N. J. Chem. Phys. 1989, 91, 4485.
Femtosecond Real-Time Probing of Reactions
description of FTS investigations of reaction 1 in terms of CW
frequency-resolved bound-free and free-free spectra has recently
been given by Krause, Shapiro, and Bersohn using quantum-
mechanical and semiclassical techniques.51 Bes wick and Jortner
have sought to clarify the time evolution for motion of localized
wave packets prepared on a dissociative PES by absorption of an
ultrashort laser photon, pointing out that the time scales for
dephasing of the initial wave packet and for bond rupture to form
spectroscopically identifiable products differ by some two orders
of magnitude.49
In this work, experimental results2-5 are compared with quantum
and classical calculations of reaction 1. The quantum-mechanical
simulation involves computation of [I—CN]4* wave packets for
various times following laser excitation in a manner analogous
to the earlier work of Williams and Imre.42 The classical de-
scription employed here makes use of the approach developed
previously by Bersohn and Zewail.62 From the transient behavior
so derived in both sets of calculations, the inversion procedure of
Bernstein and Zewail63 is applied to deduce the functional forms
of the model potential energy curves at large interfragment sep-
arations, or more accurately, the difference between PESs con-
nected by the probe laser. In this way, the sensitivity of calculated
FTS transients as a function of the nature of the two PESs involved
is examined by variation of the parameters appearing in the
analytical forms for the relevant potential energy functions.
Possible experimental ramifications of the presence of a centrifugal
barrier on the reaction path leading to final products are also
examined, and preliminary consideration is given to the type of
dynamical behavior that might be observable in the time domain.
Finally, the validity of the different theoretical approaches em-
ployed here is further examined by comparison of the results
obtained for dissociation of ICN with analogous data75 for
fragmentation of the heavier Bi2 molecule.
The paper is organized as follows. In section II the theoretical
framework underlying the quantum-dynamical and classical
calculations of FTS behavior is briefly reviewed, and an outline
is given of the main results of the potential inversion method
developed by Bernstein and Zewail;63 in addition, our selection
of PESs for calculations on ICN photodissociation is described.
The results of quantum and classical simulations of FTS spectra
for the dissociation process (la), together with inversion of these
data to the reactive potential and variation of the functional form
of the PESs are presented in section III. Summarized in section
IV are experimental and theoretical results pertaining to the
dissociation of Bi2, which are contrasted with those for ICN
dissociation. Section V comprises a summary and conclusions
and attempts to offer a broader perspective of the real-time dy-
namics that characterize direct dissociation over repulsive PESs.
II. Theoretical Methodology
Figure 1 displays schematically a simple pump-probe experi-
ment in terms of three noninteracting potential energy curves
(though the general designation “PES” is retained throughout),
the simulation of which is to be carried out. Our discussion
throughout this paper is confined to dissociation of a rigid qua-
si-diatomic molecule involving a single translatory degree of
freedom (reaction coordinate); i.e., rovibrational excitation of the
CN photofragment is considered to be negligible in comparison
to the available translational energy for product recoil. It is
therefore assumed that the short-time dynamics of the reacting
system is dominated by one-dimensional motion over a PES that
is repulsive in nature, here labeled K,(r); for dissociation of ICN,
this motion occurs along the I-CN stretching coordinate.
Measurements of nascent product-state populations at selected
=» 220-350 nm have
photolysis wavelengths over the range
indicated that the CN photofragment of reaction la (giving rise
to ground-state I(2P3/2) atoms) is produced vibrationally
(73) Pollard, W. T.; Lee, S.-Y.; Mathies, R. A. J. Chem. Phys. 1990, 92,
4012.
(74) Lin, S. H.; Fain, B.; Yeh, C. Y. Phys. Rev. A 1990, 41, 2718.
(75) Bowman, R. M.; Gerdy, J. J.; Roberts, G.; Zewail, A. H. J. Phys.
Chem. 1991, 95, 4635.
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7975
ground- and excited-state potential curves for ICN at energies E < 60
X 103 cm-1 above the electronic minimum of the molecular ground state
V0(r), illustrating the concept of FTS investigations. F,(r) and V2(r) are
given by the functional form V¡(r) = F¡° exp(-a,r) + /3, with V¡° 2.061
-
X 1010 cm-1, , = 5.1813 A-1, di = 26 130 cm-1, a2 = “ A-1, and ß2 -
50760 cm-1. For presentation purposes only a single reactive potential
V¡(r) is shown; omitted from the diagram are the several excited-state
PESs correlating with CN(X2S+) + I(2P3/2) and I(zP|/2) products at
infinite separation. The arrow labeled X, represents a vertical transition
from the o = 0 level of the ground state at the equilibrium I—CN sepa-
ration rt for a pump-laser wavelength of Xt = 306 nm, which results in
preparation on Kt(r) of a wave packet comprising a distribution of con-
tinuum eigenstates determined by the spectral profile of the laser pulse.
(Note that at this photolysis energy, the wave packet prepared by the
pump pulse initially samples classically forbidden regions of configuration
space.) The vertical transitions to the highest lying potential V2(r) la-
beled X2" and X2 represent probe-laser pulses for on-resonance (final
product) and off-resonance (transition-state) detection, respectively. A
Gaussian profile for the pump-laser pulse with fwhm = 118 cm-1 is
depicted schematically on the left ordinate. D0l (= 0,) and D02 (= ß2)
are dissociation limits for K,(r) and V2(r) measured from the v = 0 level
of K0(r).
^(¡13,14,16-19 but rotationally quite hot,13-20·2128·31 and more or less
exclusively in the ground electronic state X'2+.13,14 (In contrast,
the rotational distribution of CN product formed in reaction lb
is peaked at low quantum numbers.13-16'18-20,22·28·31) By use of a
supersonic molecular beam source to achieve internal-state cooling,
experiments carried out by Houston and co-workers19·26 and by
Nadler et a).20 have demonstrated the unimportance of initial
parent rotation as a source of the rotational excitation of CN
product;17'39'47·52·53·56·57 in any case, the rotational period of ICN
in its J = 31 quantum level, for which room-temperature popu-
lation is maximal, is longer than the time scale for recoil of the
I + CN photofragments of reaction 1 to form spectroscopically
identifiable dissociation products.2·3,5·28·47 It has been suggest-
ed,! 7-20,22,26,28,3 1,35,38,40,52-57 therefore that the v2 vibration of ICN
is of considerable importance as it dissociates, since a bent con-
figuration of the parent molecule correlates adiabatically with
rotational motion of CN at large interfragment separa-
tions.22·37·38·54·76·77
Experiments that make use of the polarized nature of laser
beams have permitted the directionality of the transition moment
involved in the initial absorption process from the ground state
to be deduced.12·22·26·28 For example, at the experimentally con-
venient photolysis wavelengths X = 266 and 248 nm, measurements
of the alignment of CN angular momentum22·26·28 indicate that
the dominant absorption transition is predominantly parallel in
(76) Ashfold, . N. R.; Macpherson, . T.; Simons, J. P. Top. Curr.
Chem. 1979, 86, 1.
(77) Felps, W. S.; Rupnik, K.; McGlynn, S. P. J. Phys. Chem. 1991, 95,
639.
7976 The Journal of Physical Chemistry, Vol, 95, No. 21, 1991
character and occurs to a PES of = 0* symmetry in Hund’s
case c ( 0, ) notation (3 0+ for (A,5) coupling), together with
a smaller perpendicular contribution arising from excitation to
a PES of 1
=
(3·' ,) symmetry, especially at the shorter
wavelength.12'22’26·28’29·31·47 The observed13*20,22'28’31 high rotational
excitation of CN arising from reaction la has been postulated
to result from a mechanism that involves nonadiabatic mixing
between an initially populated linear ( = 0+) state connecting
with spin-orbit-excited I(2Pty2) atoms at infinite separation and
one or more bent excited-state surfaces that correlate with
ground-state I(2P3/2) + CN(X2Z+) final products via the lower
energy exit channel.19·22,24"29'31'32'35'38'47'48'55 Simultaneous optical
excitation to more than one upper state of linear or bent molecular
geometries with subsequent evolution of the dissociating system
over essentially noninteracting PESs cannot be ruled out as a
possible alternative, however.
Of the numerous35·38"41'48'52"55,64 theoretical investigations that
been carried out with the aim of accounting for the observed CN
rotational energy distributions arising from both reaction channels
(la) and (lb), the following studies may be highlighted. Goldfield
et al. have modeled the A-state dissociation by means of computing
classical trajectories over model PESs, assuming initial absorption
to a linear PES and taking into account the effect of nonadiabatic
transitions between excited-state surfaces.55 These authors find
that while the results of their calculations reproduce CN rotational
energy distributions, average rotational energies and branching
ratios for reaction via both exit channels (la) and (lb)55 in a
qualitative fashion, they are unable to describe quantitatively all
aspects of the dissociation dynamics. A similar conclusion was
reached by Guo and Schatz,48 who have performed an exact
time-independent, quantum-mechanical investigation using the
coupled-channel model to calculate product rotational-state dis-
tributions, 1-atom branching ratios, and total absorption cross
sections. Satisfactory qualitative agreement with experimental
results13*20'22"26'28'29'31'64 was likewise obtained by these workers,
though it was noted48 that closer quantitative accord awaits the
availability of accurate information concerning the detailed to-
pologies of the PES(s) controlling reaction.
The results of recent ab initio calculations50 of the excited-state
potentials of ICN suggest that all relevant excited-state PESs of
ICN involved in ultraviolet absorption via the A-band continuum
may in fact possess nonlinear geometries in the Franck-Condon
region such that a bent configuration is initially adopted by the
excited parent molecule, with equilibrium ICN angles between
40° and 60°, thereby exerting a strong torque on the recoiling
CN product. The presence of a conical intersection between
excited-state surfaces located well beyond the Franck-Condon
region, in addition to the strongly bent geometries of the PESs
at shorter distances, has permitted Yabushita and Morokuma50
to reinterpret earlier experimental results12"32 in light of these
predictions and to propose a model for photodissociation of ICN
that differs substantially from those previously advocat-
ed.1 9,22,24-29,31,32,35,38,47,55 By analogy with their theoretical study
of excited-state PESs for C1CN, Reisler and colleagues have
offered further insight into the ordering and geometries of the
electronic states involved in ICN dissociation, including the
possibilities for avoided crossings between PESs and nonadiabatic
transitions.78 Dugan has also presented a model calculation that
accounts for the observed CN rotation in terms of the torque
generated by a repulsive force developed between the I and CN
photofragments acting in a bent configuration on the excited-state
potential.56·57
The angular part of the PES is neglected in this simple
treatment, however; as pointed out by Williams and Imre,42 the
dominant force in the Franck-Condon region is along the I—CN
stretching coordinate, since both excited states K,(r) and V2(r)
display a maximum or minimum along the bending coordinate
for a linear molecular geometry. Radial and angular topologies
of the excited-state PESs of ICN have also been discussed by
Benjamin and Wilson,58 and their classical trajectory calculations
(78) Bai, Y. Y.; Segal, G. A.; Reisler, H. J. Chem. Phys. 1991, 94, 331.
Roberts and Zewail
were based upon the same premise, being carried out on a model
dissociative PES with a single minimum about zero bending angle.
Our (simplified) choice of PESs for the ICN system is described
in more detail in section II.C.
Referring to Figure 1, we note that the pump laser at wave-
length , (= 306 nm as depicted) excites the ground-state wa-
vefunction from the potential V0(r) to a single repulsive excit-
ed-state potential Vfr), where a superposition of continuum ei-
genstates is formed constituting a wave packet. For ICN, the
pump laser induces absorption via the A continuum as indicated
by (la); Vfr) may possess = 1 or 0+ t3!^ or 3 0+) symmetry
and is populated by means of a perpendicular or parallel absorption
transition, respectively, from the = 0+ (1 +) ground state as
noted above. The wave packet so prepared, moving under the
influence of the repulsive force directed along the reaction co-
ordinate r, then propagates over F,(r) to form dissociation
products, during which process it is subject to the perturbation
due to the probe laser at wavelength X2 delayed with respect to
the pump-laser pulse by a time r. The probe laser excites the wave
packet on F,(r) by means of a vertical free-free transition to a
second excited-state potential F2(r), the topology of which at this
stage may be assumed to be independent of radial coordinate r
for the sake of simplicity (see section II.C). Those transition-state
configurations [I—CN]** that allow for absorption of probe-laser
light define a detection “window”, or optically-coupled region,4,62,63
centered about X2 and of spectral width determined by the tem-
poral duration of the probe laser.
The PESs Vfr) and V2(r) correlate with I(2P3/2) + CN(X22+)
and I(2P3/2) + CN(B22+) asymptotic product states, respectively.
The influence of additional low-lying repulsive PESs Vfr), for
instance those of = 2 (3 2) and 0" (3 0-) symmetry leading to
ground-state I(2P3/2) product via reaction la, are omitted from
Figure 1, since possible nonadiabatic interactions involving such
surfaces and Vfr) have been considered19'22'24"29·31,32'35'38·47'55 to
occur within the Franck-Condon region at interfragment sepa-
rations shorter than those accessible with an experimental pump
wavelength of X, = 306 nm. In this context, however, it may be
noted that the existence of a conical intersection between the
= 0+
(3 +) and = 1 ( ,) potential curves (that correlate with
I(2P1/2) and I(2P3/2) atoms at infinite separation, respectively) at
an I—CN distance of r 3.32 Á has recently been predicted,50
~
which would play an important role in governing the dissociation
dynamics at shorter photolysis wavelengths where reaction channel
lb is accessible (see above).
The final wave packet on V2(r) can be monitored by emission
of resonance fluorescence back to F^r),1*11 permitting elucidation
of the real-time dynamics of the dissociation process by detection
of such fluorescence as a function of the pump-probe time delay
t: this is the essence of the FTS experiment. Variation of the
probe-laser wavelength allows the time-evolution of the wave
packet propagating over F,(r) to be interrogated at different spatial
coordinates, since in general the energy separation between Vfr)
and F2(r) will not be constant as a function of dissociation co-
ordinate r.
A. Quantum Dynamics. The quantum dynamical treatment
employed in this paper to simulate the FTS pump-probe exper-
iment is that of second-order time-dependent perturbation theory.79
This method has previously been invoked and developed by
Williams and Imre,42 Metiu and co-workers,80"86 and others to
study the behavior of gas-phase dissociation reactions in the time
domain. The time-dependent approach pioneered by Heller and
co-workers, using Gaussian wave packets, illuminated the analysis
of Light·, Clarendon Press: Oxford,
(79) Loudon, R. The Quantum Theory
1973; Chapter 11, p 279.
(80) Engel, V.; Metiu, H.; Almeida, R.; Marcus, R. A.; Zewail, A. H.
Chem. Phys. Lett. 1988, 152, 1.
(81) Engel, V.; Metiu, H. J. Chem. Phys. 1989, 90, 6116.
(82) Engel, V.; Metiu, H. J. Chem. Phys. 1989, 91, 1596.
(83) Engel, V.; Schinke, R.; Hennig, S.; Metiu, H. J. Chem. Phys. 1990,
92, 1.
(84) Engel, V.; Metiu, H. J. Chem. Phys. 1990, 92, 2317.
(85) Metiu, H.; Engel, V. J. Chem. Phys. 1990, 93, 5693.
(86) Metiu, H.; Engel, V. J. Opt. Soc. Am. B 1990, 7, 1709.
Femtosecond Real-Time Probing of Reactions
of dynamics in real time,45·66·87,88 and Kinsey and co-workers have
elegantly applied the method to examine molecular fragmenta-
tion.89
The nuclear wave function |^2(z)) created on the potential V2
by absorption of pump and probe photons is calculated from the
expression79
\Ht)> =
H'/ )2 J' dr2 x
f d/j 7'2(f-f2)í/2|(í2)7'i(í2-íi)t/]o(f|) ß (-/ „ ,)|^)
Here |^„) represents a nuclear eigenstate of the uth vibrational
of the ground electronic state with a phase factor ß (- „/,).
level
Wave functions are propagated by the operators , whose explicit
form is
=
7,(Z) exp(-/ZZ,z)
with Hamiltonian operators H, given by
H,= \i)[K+ K,](z|
where K and V¡ are the kinetic and potential energy operators,
respectively. Uy(tk) represents the time-dependent perturbation
caused by the fcth laser pulse, which optically couples electronic
states |i) and [/):
U,j{tk)
=
µ,/ )· *
where µ,/r) is the transition dipole moment operator connecting
state l/) to |i). In the absence of information concerning the
variation of µ,^( ) with coordinate r, the Condon approximation
is assumed throughout this work; i.e., pdr) = µ /) (/|. Ek(tk) is
the electric field vector of the radiation field due to the fcth laser
pulse:
=
Ek0k) gk(tk)Ek° exp(iwktk)
the temporal lineshape gk(tk) of which is taken to be Gaussian
for both laser pulses.
gk(tk) -
exp[-(Z* -
tk°)/ak2]
The time delay between pump- (k 1) and probe-laser (k =
=
2) pulses is defined in the usual way as the difference between
the times at which the intensities reach their maximum values:
=
r2° r,°.
-
Equation 2 indicates that at time tx the perturbation due to the
pump photon, lZ10(f,), promotes the ground-state eigenfunction
| ?„) (- „ ,) to the electronic state |1). The wave function
|^ ( )) so created is then propagated over Vfr) by action of the
operator Tft2-t¡) for a time duration t2 r,. At time Z2, the
-
perturbation U2i(t2) excites a transition between electronic states
¡1) and |2), corresponding to absorption of a probe-laser photon.
The resulting wave function \ 2( ) > is subsequently propagated
by T2(t t2) until some final time t. Following our earlier cal-
-
culations of Hgl2 wave packets,90 both Fourier-transform-limited
laser pulses are arbitrarily truncated at ±2<r* so that the operators
UMk) act on the appropriate wave function over a total period
of time 4 *; the length of time over which the propagation op-
erators ,( ) are applied in eq 2 is thus reduced proportionately.
The complete promotion-propagation sequence therefore begins
at time t = -2a, (start of pump-laser pulse) and finishes at time
Z = +2 2 (end of probe-laser pulse). In what follows, we shall
be concerned with only the total emission intensity ( ; 2) from
the electronic state |2). This is proportional to the norm
(tfoiOhMO) of the final wave packet, representing the probability
of locating the system in state |2) at a time t immediately following
the action of the probe-laser pulse.
(87) Heller, E. J. J. Chem. Phys. 1975, 62, 1544.
(88) Heller, E. J. Acc. Chem. Res. 1981, 14, 368.
(89) Imre, D.; Kinsey, J. L.; Sinha, A.; Krenos, J. J. Phys. Chem. 1984,
88, 3956.
(90) Gruebele, M.; Roberts, G.; Zewail, A. H. Philos. Trans. R. Soc.
London, A 1990, 332, 223.
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7977
Wave packet propagation was carried out by using the split-
operator technique developed by Feit and co-workers.91"93 Nu-
merical calculations were carried out such that eq 2 could be
implemented with pump and probe pulses overlapped in time and
were performed on a grid of 2048,4096, or 8192 points, depending
upon the kinetic energy of the wave packet and the distance range
involved. As noted in a previous publication,90 care was taken
to sample above the Nyquist limit in both momentum and co-
ordinate space so as to mitigate against aliasing and edge effects
(2) of the discretized wave functions. Convergence was tested for
in the usual manner by having the number of discretizations and
the time step. For a propagation period of 300-500 fs, converged
wave functions were obtained for time steps At < 1/(50A£), where
AE is the characteristic energy scale of the problem. In all
calculations, the initial wave function ß ( ,, 1)|^ ,) was taken
to be the Gaussian form of the v = 0 level of the ground electronic
(3) state.
B. Classical Mechanics. The classical-mechanical analysis of
ICN dissociation adopted in this paper employs the method
(4) prescribed by Bersohn and Zewail to derive an expression for the
explicit time dependence of the probe-pulse absorption A(t) for
classical motion of the reactive system over Vfl).62 In this
treatment, the first (pump) absorption step results in localized
excitation of ICN by means of an initial laser pulse that is a
function in time, while the finite spectral bandwidth of the
(5) “temporally short” probe-laser pulse is considered to project a
detection window (or optically coupled region) onto the potential
for fragment separation such that maximum probe absorption
occurs at some configuration r* along the dissociation coordinate.
Fried and Mukamel have pointed out that spectral convolution
of the absorption profile by the probe pulse is appropriate in those
instances where the pump and probe pulses are short in comparison
to the time dependence of the nuclear dynamics; temporal con-
volution is valid when the pulses are longer than the time scale
(6) for dephasing (given by the inverse line width of the overall
absorption).61 This dephasing has a direct influence on the co-
herence effect discussed and ruled out by experiment:5 in these
experiments, the coherence (and dephasing) time is much shorter
(7) than the laser pulse widths.
For any distance r along the reactive potential Vfr), absorption
of the probe laser pulse may be written62
>i(r) =
Cexp!-(ln 2)[(K2(r) -
K,(r))-
(V2(r*) -
Vfr*))]2/(Av/2)2) (8)
where C is an arbitrary constant (set equal to unity) and the
spectral profile of the probe laser is taken to be Gaussian with
fwhm = Av. Equation 8 represents spectral convolution of the
probe-pulse absorption A(r). Bersohn and Zewail62 have noted
that Av for femtosecond laser pulses will exceed the natural line
width of free fragments by several orders of magnitude, so that
an intrinsically sharp absorption would appear to be Gaussian in
shape.
Transient behavior is determined by the classical time evolution
of a particle
over the PES V¡ (r) governing dissociation, the ap-
propriate equation of motion for which is
(u/2)(dr/dt')2 =
£av
-
Vfr) (9)
where £av is the kinetic energy available to separating fragments
of reduced mass µ in the center-of-mass frame relative to the
dissociation limit of K,(r). The distance traveled by a point mass
as function of time is then given by
r, =
r0 + y
Jo'[l
-
K,(r)/£av]V2 dr' (10)
Equation 10 can be integrated analytically in the case of a repulsive
potential V¡(r) given by the simple exponential form of eq 16,
yielding the expression
(91) Fleck, J. A., Jr.; Morris, J. R.; Feit, M. D. Appl. Phys. 1976,10,129.
(92) Feit, M. D.; Fleck, J. A., Jr.; Steiger, A. J. Comput. Phys. 1982,47,
412.
(93) Feit, M. D.; Fleck, J. A., Jr. J. Chem. Phys. 1983, 78, 301.
7978 The Journal of Physical Chemistry, Vol. 95, No. 21, ¡991
r, =
r0- (l/ ,) In [sech2 (vtaj2)]
Here, t is the time taken by a reactive trajectory on F,(r) to reach
the position r measured from t = 0 at the initial coordinate r0
determined by classical Franck-Condon absorption from the
ground state; t* is therefore the time corresponding to r-r*. The
terminal velocity (2£„ /µ)'/2 is the classical counterpart of
-
the asymptotic (long-time) group velocity of the quantum-dy-
namical wave packet. 1 /< is the so-called length or range pa-
rameter of the exponential potential function Vfr) (see eq 16),
and represents the distance by which potential energy has de-
creased to 1 /e of its value at the position r0.
A straightforward manipulation of eqs 8 and 11 leads to an
analytical solution for the time dependence of absorption of the
probe-laser pulse given by
A(t) = C expKln 2)[/( , *)/( ?/2)]2|
where
=
K2(/)[£,v/K,(/)]“*/“' sech2-/"· x
ft(i*)[£av/^i(f*)]“2/a| sech2-/"· x*
£av(sech2 x
F,(z) and K2(i) are the potential energy curves of Figure
pressed as a function of time, while x = and x* = ,/2
when t = t*. If it is assumed that the high-lying potential V2(r)
populated by the probe laser is independent of position along the
reaction coordinate, meaning that a2 = ” Á"1 (see eq 16), then
eq 12 reduces to the simpler form
A(t) = C exp|-(ln 2)[£'av(sech2 x* -
sech2
The distributions of both trajectory starting times and finishing
(probing) times incurred by the use of laser pulses of finite tem-
poral duration can be accounted for by convolution of the ab-
sorption A(t) of eq 12 with the temporal lineshapes gk(tk) of the
pump and probe lasers:
A(t) =
A(t2°
-
t,°) = -
where gl2(r) represents the cross-correlation function of pump and
probe pulses. Thus the initially imposed criterion of -function
laser pulses is removed, which provides a more valid comparison
with experiment. A(r) is taken to represent the observed LIF
signal, which we designate /( ; 2) in accordance with an earlier
notation.63 This temporal convolution procedure is of course
important as the duration of the laser pulse widths becomes
comparable to the time scale of the dynamics of dissociation, as
pointed out previously.4·5 Conversely, if the pulses are much
shorter than the time required for nuclear recoil (but longer than
the dephasing time) then convolution becomes unimportant.
Examples of situations where the relevant reaction dynamics occur
over much longer time scales than the laser pulse widths have been
reported for dissociation of Bi2,75 12,94-97 Nal,98-102 and Hgl2.103·104
(94) Bowman, R. M.; Dantus, M.; Zewail, A. H. Chem. Phys. Lett. 1990,
161, 297.
(95) Dantus, M.; Bowman, R. M.; Zewail, A. H. Nature (London) 1990,
343, 737.
(96) Gerdy, J. J.; Dantus, M.; Bowman, R. M.; Zewail, A. H. Chem. Phys.
Lett. 1990, 171, 1.
(97) Bowman, R. M.; Dantus, M.; Zewail, A. H. Chem. Phys. Lett. 1990,
174, 546.
(98) Rose, T. S.; Rosker, M. J.; Zewail, A. H. J. Chem. Phys. 1988, 88,
6672.
(99) Rosker, M. J.; Rose, T. S.; Zewail, A. H. Chem. Phys. Lett. 1988,
146, 175.
(100) Rose, T. S.; Rosker, M. J.; Zewail, A. H. J. Chem. Phys. 1989, 91,
7415.
(101) Cong, P.; Mokhtari, A.; Zewail, A. H. Chem. Phys. Lett. 1990,172,
109.
(102) Mokhtari, A.; Cong, P.; Herek, J. L.; Zewail, A. H. Nature (Lon-
don) 1990, 348, 225.
(103) Bowman, R. M.; Dantus, M.; Zewail, A. H. Chem. Phys. Lett. 1989,
156, 131.
Roberts and Zewail
(11) Theoretical expressions for A(t) applicable for arbitrary pulse
conditions have recently been derived by Fried and Mukamel.61
C. Choice of PESs. In this section, we indicate the sources
from which the simple parametrized forms of the potential energy
functions for the electronic states |0>, |1), and |2) were selected.
The ground-state potential V0(r) is assumed to be harmonic,
since optical excitation of the thermal population in the lowest
vibrational level only is treated in this work, as appropriate for
the room-temperature experimental conditions employed.1-6 The
generally accepted value of rt = 2.745 Á105 dating back to 1936106*
was taken to be the equilibrium interfragment separation between
the I atom and center of mass of CN,l06b while the value , =
451.5 cm-1 determined spectroscopically by Penney and Suther-
land106* was employed as the fundamental oscillation frequency
of the NC—I stretching vibration.
As a simple characterization of the V¡(r) and V2(r) potentials
(12) of ICN we invoke a repulsive exponential curve:
Vfj) =
Vt° exp(-a,r) + ft (16)
-
Values of a, = 5.1813 Á-1 and K° = 2.061 X 1010 cm-1 were
-
employed in this work, being the parameters obtained by Bersohn
-
sech2 x*) (13) and Zewail62 from a consideration of spectroscopic investigations
of the A ·*- X band system of ICN.24·111 From an empirical point
1 ex- of view, and following these same authors,62 it is initially considered
vt*afl that | Vfr) F,(r*)| »\V2(r) V2(r*)\ for all values of r* accessed
- -
by tuning the probe-laser wavelength, i.e. that the shape of V2(r)
is independent of reaction coordinate at distances greater than
the Franck-Condon region for absorption of pump-laser light.
Accordingly, a value of 2 = == A-1 was employed for the majority
of the calculations reported in this work (so that V2(r) is simply
)/( /2)]2) (14)
ft). More realistic (finite) values of a2 were also tried, however,
as described in section III.D. ft and ft represent, of course, the
dissociation energies D0l and D02 shown in Figure 1; values of ft
= 26 130 cm-1 and ft = 50 760 cm-1 were used in the present
calculations.62·112·113
In order to obtain the correct absolute values of X2 employed
in the experiments of Dantus et al.,5 it was found necessary to
include the effect of the rotational energy content of the diatomic
t) it (15)
photoproduct. Commensurate with on-resonance (X2“) probing
at the band head of the P branch of the 2 + ·*- 2 + (0,0) band
(104) Dantus, M.; Bowman, R. M.; Gruebele, M.; Zewail, A. H. J. Chem.
Phys. 1989, 91, 7437.
(105) Herzberg, G. Molecular Spectra and Molecular Structure II: In-
frared and Raman Spectra of Polyatomic Molecules·, Van Nostrand Reinhold:
New York, 1945; Chapter 2, p 174.
(106) (a) Penney, W. G.; Sutherland, G. B. B. M. Proc. R. Soc. London,
A 1936,156, 339. (b) The value rt = 2.745 A has been employed by several
research groups during recent years (see, for example, refs 3, 5, 19, 26-32,
35, 38,40, and 55 among others); its current usage appears to stem from the
early theoretical study of ICN dissociation presented by Holdy, Klotz, and
Wilson in 1970.64 This value was obtained by these workers from the struc-
tural parameters for ICN listed by Herzberg in 1945,105 which were themselves
taken from the gas-phase spectroscopic study of Penney and Sutherland
reported in 1936.106* In order to derive force constants for the vibrational
modes of ICN, these authors employed an estimate of r^-c, « 2.12 A as the
equilibrium internuclear separation between I and C atoms, calculated by
adding the difference between the ionic radii of I and Cl to an earlier de-
termination of the C-Cl separation in CC14 published in 1935,107 while for
the distance between C and N atoms, the value r^c_N) * 1.15 A was taken10**
from infrared absorption measurements on HCN, also carried out in 1935.108
We note that somewhat more recent estimates of · - = 1.9921 ± 0.0002
A and r^c-N) = 1.1604 ± 0.0003 A determined by microwave spectroscopy109
lead to the value rt = 2.616 A as the I-CN equilibrium separation. This result
is in agreement with the spectroscopic parameters for ICN listed in the latest
edition of the JANAF thermochemical tables.110
(107) Sutton, L. E.; Brockway, L. O. J. Am. Chem. Soc. 1935, 57, 473.
(108) Bartunek, P. F.; Barker, E. F. Phys. Rev. 1935, 48, 516.
(109) Cazzoli, G.; Degli Esposti, C.; Pavero, P. G. J. Mol. Struct. 1978,
48, 1.
(110) Chase, M. W., Jr.; Davies, C. A.; Downey, J. R., Jr.; Frurip, D. J.;
McDonald, R. A.; Syverud, A. N. J. Phys. Chem. Ref. Data, Suppl. 1985,
14, 601 (JANAF Thermochemical Tables, 3rd ed., Part 1).
(111) King, G. W.; Richardson, A. W. J. Mol. Spectrosc. 1966, 21, 339.
(112) Davis, D. D.; Okabe, H. J. Chem. Phys. 1968, 49, 5526.
(113) Huber, K. P.; Herzberg, G. Molecular Spectra and Molecular
Structure IV: Constants of Diatomic Molecules·, Van Nostrand Reinhold:
New York, 1979.
Femtosecond Real-Time Probing of Reactions
system,14,15·67'70 N" = 25 is adopted as the most populated ro-
tational level of the CN(X22+) ground electronic state16"18 re-
sulting from the torques experienced by the parent molecule on
dissociation. Furthermore, rotational excitation of the radical is
considered to be independent of the NC-I stretching coordinate.
(That is, the time development of angular momentum during the
dissociation process is neglected.)
Figure 1 displays the minimum number of PESs required for
description of the FTS experiment. It was pointed out in section
1 that at a pump wavelength of !
= 306 nm the exit channel
(lb)
is effectively closed, with only a negligible fraction of reactive
trajectories proceeding to I(2Pi/2) product,12,13·17·18·22"25,32 whereas
at the shorter wavelengths ! = 295 and 285 nm, reactions la
and 1 b leading to formation of both spin-orbit levels of atomic
iodine are energetically feasible.62,112,113 Most calculations reported
in this paper were carried out for a pump wavelength of = 306
nm, well to the low-energy side of the absorption maximum for
the A continuum located at X = 251.3 nm,77 though a number
of calculated transients for reaction la were also obtained for
higher photolysis energies using the same potential curves described
above. From the laser excitation energies and dissociation limit
ß given earlier, optical excitation at X[
=
306, 295, and 285 nm
is found to correspond to total available kinetic energies for
fragment separation via the lower-lying exit channel (la) of £av
= 6550, 7769, and 8958 cm"1,
compared to the spin-orbit splitting
in atomic iodine of £(2P,/2) £(2P3/2) = 7603 cm'1.114 The
-
terminal velocities for I(2P3/2) + CN(X22+) separation are thus
readily determined as v = 0.0269, 0.0293, and 0.0315 Á fs'1,
respectively, for the three photolysis wavelengths.
D. Inversion to PES and the Classical Limit. Inversion to the
PES from computed FTS data was carried out following the
methodology put forward by Bernstein and Zewail.63 Recovery
of the functional form of the potential energy function Vft) for
the first excited state expressed as a function of time from de-
convolved FTS transients of /(f;X2) versus t is readily affected by
a straightforward analysis of long-time LIF signal intensities for
different probe laser wavelengths X2. Detection of transient
[I'-CN]*4' species evolving over different regions of configuration
space on V,(r) leads to an asymptotic fluorescence signal that is
determined by the spectral intensity of the (blue) wing of the probe
laser; LIF signals monitored at long delay times for different X2
thus project into the frequency domain the effective intensity
spectrum of the probe-laser pulse.63 It may be pointed out in this
regard that asymptotic values of <^2(i) IV^M) calculated by eq
2 instead reflect the spectral profile of the time-dependent electric
field vector E2(i2) of the probe-laser pulse (see eq 6), rather than
its intensity /2(f2) per se (which in any case is trivially related to
^2(^2))· For both quantum and classical simulations, therefore,
the temporal potential V\(t) can be related to the spectral dis-
tribution of the probe laser about its nominal frequency v2 and
the detuning increment =
v2 v2 with respect to the on-res-
- III. Results
onance probe frequency P2*.
For a Gaussian probe-laser profile and an upper-state PES V2(r)
accessed by the probe pulse that is assumed to show no dependence
on interfragment separation r, considerations of this nature lead
to an expression for Vft) of the form
V}(t) = ± ( ?/2)|1 [C//(f;X2)]/ln 2|V2 (17)
where now /(t;X2) represents deconvolved FTS data points.
Equation 11 permits Vft) to be conveniently transformed to Vfr)
and vice versa. Application of eq 17 to yield a faithful repre-
sentation potential energy function governing reaction from ex-
perimental measurements necessitates that various assumptions
are made concerning the nature of the time development of the
dissociative process. The inversion procedure outlined above
requires63 that the time evolution of the reacting system is governed
by the laws of classical mechanics so that the photofragmentation
process can be viewed as the motion executed by a heavy particle
traversing the controlling PES. In reality, the first (pump) ex-
(114) Moore, C. E. Atomic Energy Levels, Natl. Stand. Ref. Data Ser.
(U.S., Natl. Bur. Stand.) 1971, 35, 106.
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7979
citation process transfers population from the ground state to the
excited PES K, (r) over a range of times and consequently with
a spread of kinetic energies corresponding to different initial
starting coordinates on the upper-state PES.
In applying eq 17 to deduce Vft) from FTS data therefore,
it is assumed that the initially created wave packet describing the
separation of products is highly localized and remains so during
the course of the dissociation process. That is to say, the width
of the wave packet Ar (= l/2[(h/Ap)2 + (2< /µ)2]1/2 for a
Gaussian packet, where Ap is the corresponding momentum
distribution) stays essentially constant and that the degree of
spreading of the wave packet as a function of time dAr/dt (d2-
{Ar)2/dt2 (2/µ2)[( )2 ( /·)2µ K/'fr)]1 ls) is negligible over
~
-
the time period during which the system evolves to final product
states (or alternatively, that changes in the distribution of kinetic
energies of the initial wave packet with time are small). The width
Ar of the wave packet may or may not, however, be narrower than
the range of spatial coordinates on the PES viewed 1jy the
probe-laser pulse.
Furthermore, the transition dipole moment <2|u2l(r)|l) between
the electronic states optically connected by the probe laser is
assumed to be independent of spatial coordinate r (see section
II. A). The vertical probe transition is also presumed to conserve
the momentum of the separating products; i.e., that no change
in the internal motion of the probed fragment is induced as a result
of the action of the probe laser pulse. A more complete description
of the asymptotic LIF intensities would take into account the effect
of probing a (nonstatistical) rovibrational energy distribution of
CN(X22+) product species.
Finally, it is stressed that application of eq 17 to FTS data
strictly yields a difference in potential energy | 21(/)| = \V2(t)
-
K,(i)| between the two electronic states connected by the probe
laser as a function of time (or interfragment distance), rather than
the potential controlling the dissociation dynamics alone. FTS
experiments that involve systematic variation of the pump-laser
wavelength independently of that of the probe, thus permitting
control of the excess energy above threshold for dissociation, do
allow separation of K,(r) and V2(r) to a certain degree of self-
consistency,63 as has been undertaken in a previous FTS study
of the topologies of the low-lying excited-state PESs involved in
the predissociation of Nal for instance.116,117 An analysis pro-
cedure for extracting the topologies of bound-state potential energy
curves for electronically excited I2(B3n0+u)94,95 and ICl(A3n,)118
from FTS measurements has recently been adopted that makes
use of Fourier transformation and RKR techniques.119,120 The
inversion procedure outlined above has also been applied to dif-
ferent functional forms of both excited-state PESs Vfr) and V2(r),
examples of which have been discussed in the paper of Bernstein
and Zewail.63
and Discussion
A. Quantum Calculations. Figure 2 shows snapshots of the
time-dependent wave packet IV'iM) as it evolves over the PES
Vt(r) at various times following laser excitation of ground-state
ICN at X, = 306 nm with a Gaussian pump pulse of fwhm = 125
fs. The potential energy functions Vfr) and V2(r) used in these
simulations are given by eq 16 with the parameters given in section
II.C. As indicated in Figure 1, and discussed previously by Fisher
et al.,17,18 optical excitation of ICN at X] = 306 nm is a classically
forbidden process (K,(r) -v^ 7525 cm'1 for r = rt), so that initial
motion of the wave packet along the dissociation coordinate is
dominated by tunneling through the inner repulsive limb of the
(115) Messiah, A. Quantum Mechanics; North-Holland: Amsterdam,
1966; Vol. I, Chapter VI, pp 216-222.
(116) Zewail, A. H. J. Chem. Soc., Faraday Trans. 2, submitted for
publication.
(117) Cong, P.; Herek, J. L.; Mohktari, A.; Zewail, A. H. Unpublished
results.
(118) Janssen, . . M.; Bowman, R. M.; Zewail, A. H. Chem. Phys.
Lett. 1990, 172, 99.
(119) Gruebele, M.; Roberts, G.; Dantus, M.; Bowman, R. M. Chem.
Phys. Lett. 1990, 166, 459.
(120) Bernstein, R. B.; Zewail, A. H. Chem. Phys. Lett. 1990,170, 321.
7980 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 Roberts and Zewail

2 4 6 8 10 12 14
r/A
**
Figure 2. [I—CN] wave packets. Time evolution of the wavefunction
IV-itO) over the PES K,(r) of Figure 1 following excitation at ! 306
=

nm by a Gaussian-shaped pump-laser pulse of fwhm = 125 fs centerd

at ( = 0 fs. Figure 3. Time-dependent [I—CN]** population on K,(r). Plot of the
population (^iMI^fz)) on the first excited PES V¡(r) of Figure 1 as a
excited-state potential. Some 50 fs after the perturbation due to function of time following laser photolysis at , = 306 nm with a
the pump laser begins, the expectation value (r) for |^,( )) is (r) Gaussian pump pulse of fwhm = 125 fs centered at t = 0 fs.
=
ra« 2.9 A, where r0 is the classical turning point on Vfr) for
this excitation energy (see section II.B).
The wave function grows during the period (300 fs) over which
the first laser pulse pumps more population to the excited state,
achieving an approximately Gaussian shape at the end of this time.
It then propagates out to larger values of r as time proceeds,
retaining its shape with very little spreading for t < 300 fs, at which
time the wave packet samples regions of Vfr) corresponding to
an average separation of (r) = 10.7 A along the I—CN inter-
fragment coordinate, approximately 4 times longer than the
ground-state equilibrium distance.105,106 Noteworthy in our view
is the fact that |^,(z)> begins to sample the asymptotic region of
the PES, where Vfr) is < 50 cm"1 above the dissociation limit,
after only some 50 fs, i.e. while the pump laser is still interacting
with the system. By the time the perturbation due to the pump
laser is complete at t = 150 fs, | ,( )) is centered about an average
position (r) = 6.7 A on the reaction path and extends over a range
of radial coordinates isr 3.4 A (measured at fwhm). Up until
~

this time, the wave packet experiences a large variation in potential

energy over a small change in r (Vfr)/cm"1: = 13 717 at r
=

rt = 2.745 A; = £av » 6550 at r = r0 = 2.89 A; and « 1.73 X r/fs

10'5 at r = 6.7 A), giving rise to severe broadening of the ab-
sorption spectrum. The greater part of the nuclear recoil process
leading to final product states, however, occurs over the long-range
part of the potential at distances r > 6.7 A, and such motion takes
a much longer time to reach completion. Beswick and Jortner
realized this point49 and Fried and Mukamel have shown how the
“tail” of the wave function can be monitored at long times.59"61
As noted in section II.B and shown in Figure 2, the finite pulse
width of the pump laser and its convolution with the early-time
dynamics clearly play an important role in determining the initial
form of the wave packet | |( )> on a purely repulsive potential
such as Vfr), and can be handled properly both theoretically and
experimentally as described below (see also section IV). The
important point, however, is that a detection window62,63 is pro-
jected onto the reactive potential by the probe laser (in this case
of width = 118 cm"1 for a Gaussian pulse of fwhm = 125 fs
in the time domain) that enables the evolution of the wave packet
to be monitored in real time.
Displayed in Figure 3 is a graph of the excited-state population
< ( )| ( )) on the potential V,(r) as a function of time following
, = 306 nm pumping. An initial rise in population is followed
by a slight decrease to some steady-state level, indicative of
off-resonance excitation to the upper electronic state in relation
to the absorption maximum at = 251.3 nm,77 as noted previously
by Williams and Imre.42
Plots of ( 2( )| 2( )) versus time delay r, representing the type
of time-resolved laser-induced fluorescence spectra obtained by
Figure 4. Transient behavior calculated by quantum dynamics. Graphs
of the norm of the wavefunction |^2(f)) created on V2(r) by action of the
probe laser, representing the total fluorescence signal, versus pump-probe
time delay for a pump wavelength of , = 306 nm and various probe
wavelengths (X2, nm): (i) 388.5; (ii) 388.9; (iii) 389.8; (iv) 390.4; (v)
391.4. Both transform-limited laser pulses have Gaussian temporal
profiles of fwhm
= 125 fs, and values of <^2(Z)|^2(f)> are normalized with
respect to the long-time asymptote of the on-resonance signal (i). Par-
ametrized forms of K|(r) and V2(r) are those given in the caption to
Figure 1. Note the different long-time values of <^2( )| 2( )) compared
to A(t) shown in Figure 5 (see text for discussion). This difference
reflects only the choice of the temporal width of E2(t2) and /2(Z2), but the
results to compare with experiments are not, of course, subject to this
choice. (See Figure 6 for inversion of FTS transients to the PES.)
the FTS technique,1"11 are displayed in Figure 4 for a pump
wavelength of X[ = 306 nm and five probe wavelengths, chosen
to match those employed in the previous experimental measure-
ments reported by our group.5 The shapes of these curves have
been discussed in detail elsewhere;2"11·42"44,51,58"60,62,63 here we wish
to highlight only a few points.
First, the calculated transients of Figure 4 are in general accord
with both the experimental measurements of Dantus, Rosker, and
Zewail2"5 and with the results of earlier quantum-dynamical42,44,51
and classical4,5,58"63 calculations. We note that the calculated
on-resonance signal, labeled (i) in Figure 4, reaches half-maximum
intensity after approximately 60 fs. According to the classical
description of section II.B, such a time represents the period
Femtosecond Real-Time Probing of Reactions
required for the dissociating system to reach that point on the
exponentially repulsive PES where K,(r) = /2 cm-1,4-62 pre-
viously designated3-5·7"10 as the clocking time t1j/2· As discussed
in section III.D, ti/2 is the dissociation time for bond rupture within
the framework of real-time measurements; as the spectral width
of the probe-laser pulse is made increasingly narrow, the rise to
the asymptotic value of an on-resonance FTS measurement be-
comes consequently sharper, cumulating in an instantaneous
step-function response in the limit that tends to zero ( -function
frequency spectrum) for probe pulses of infinite duration in the
time domain. At a time delay of = 1/2 = 60 fs, the expectation
value (r) of the wave packet | ( )) on Vfr) is (r) -
4.1 Á,
corresponding exactly with the classical value r^ = 4.1 Á given
by eq 11.
Calculations analogous to that displayed as Figure 4, curve (i),
carried out for pump wavelengths , = 295 and 285 nm, resulted
in on-resonance transients characterized by values of t^2 57
and 55 fs, respectively, reflecting the influence of increasing recoil
velocity for separation of products at shorter photolysis wavelengths
on the calculated dissociation time (see eq 18 below). That values
of t1/2 decrease only by some 5 fs when the total available kinetic
energy £av for fragment separation is increased by some 2410 cm-1
from £av » 6550 cm-1 ( , = 306 nm) to £av« 8960 cm-1 (Xj =
285 nm) is merely a reflection of the small range parameter a,-1
= 0.193 Á employed to construct the model PES K,(r), which
results in a large PE gradient dVx{r)/dr at distances smaller than
about 3 Á (and which determines the early time dynamical be-
havior of the reaction).
The dissociation times reported above are much shorter than
the values tIjZ2 = 205 ± 303-5 and 160 ± 305 fs observed exper-
imentally at pump wavelengths , = 306 and 285 nm. This may
be expected given the fact that the length parameter of our model
V¡(r) potential is some 4 times shorter than the value a,-1 = 0.8
Á derived by Bantus et al. from their on-resonance “clocking”
measurements.3-5 Indeed, when the parameters of eq 16 for K,(r)
are changed to ax = 1.25 Á-1 and K,° = 2.4272 X 105 cm-1 (the
latter chosen such that the classical turning point of the PES at
an energy £av above the dissociation limit for , = 306 nm ex-
citation is coincident with that for V¡(r) shown in Figure 1), values
of t1/2 == 185, 175, and 165 fs are determined for pump wave-
lengths , = 306, 295, and 285 nm, respectively. Taking due
account of the different CN(X2S+) product rotational energy
distributions at different photolysis wavelengths,13-20,26 the ex-
perimental values of /2 reported by Bantus et al.5 at X, = 306
and 285 nm were found to scale with the same value of af1 =
0.8 Á, indicating that fragment recoil velocity is the predominant
factor in determining r,/2 rather than the competing effect of
increased separation between r0 and the optically coupled region
provided by the probe laser when the pump energy is increased.
These data were therefore considered5 to be consistent with the
fact that (strong) interactions between the PES of = 0+ (3 0+)
symmetry leading to I(2Pw2) atomic product and those of =
0" (3 0-), 1 (3 ,), and 2 (3 2) symmetry giving rise to I(2P3/2)
atoms occur at interfragment distances shorter than r0 for X[ =
285 nm excitation (where I(2P,/2) atoms are also energetically
accessible), i.e. close to the Franck-Condon region. Such a
conclusion would be in agreement with the model potential curves
recently proposed by Black et al.31 as a result of their sub-Doppler
LIF measurements at X, = 249 nm (though no I—CN distance
scale is given in Figure 20 of that work31).
In contrast, recently reported ab initio
computations50 reveal
the presence at I—CN separations r =» 3.32 A of a conical in-
tersection involving the PESs of = 0+ (3 +) and = 1 (* ,)
symmetry (the latter connecting with ground-state I(2P3/2) atoms),
as discussed in section II. The PES of = 0+ (3 0+) symmetry
has also been computed to possess a substantial attractive well
some 3630 cm-1 in depth with a minimum situated at about r =
3.22 Á.50 The region of such an intersection between surfaces
could be traversed by [I—CN]4* wave packets prepared by
pump-laser light at X, = 306, 295, and 285 nm, though on strictly
energetic grounds, final I(2P|/2) + CN(X22+) products can only
be reached from v = 0 ground-state ICN by using pump wave-
The Journal of Physical Chemistry, yol. 95, No. 21, ¡991 7981
lengths of X[ = 295 and 285 nm (see section II.C). At this point,
we feel able only to recall that no direct evidence supporting the
presence of one or more surface intersections at distances beyond
the Franck-Condon region has been obtained from FTS mea-
surements;2-5 delays in the appearance of the free CN product
of reaction lb and/or resonance-type behavior (such as has been
observed hitherto in the dissociation of Nal,98-102 Hgl2,103,104 and
CH3I121 for example) might be expected5 to result from reactive
trajectories that sample those regions of configuration space where
diabatic surfaces intersect en route to dissociation products. The
implications of the possible location of a potential minimum along
the dissociation coordinate in relation to FTS measurements have
been discussed in detail elsewhere.63
The off-resonance fluorescence signals of Figure 4, denoted
(ii)-(v), exhibit peak intensities that shift to shorter delay times
with increasing probe-laser wavelength X2. Within the frame-
work of the classical model outlined in section II. B, this behavior
has previously been interpreted2,4,5,7,11,62,63 in terms of detection
of [I—CN]4* transition-state configurations across a range of
coordinate positions on the reactive PES. Deconvolution of the
combined pump- and probe-laser intensity profiles from the data
shown in Figure 4 indicates that the time taken for the [I—CN]4*
moiety to traverse the fwhm of the off-resonance spectra is about
5-15 fs, depending upon the off-resonance probe-laser frequency.
Experimentally, [I-CN]4* configurations have been reported to
persist for approximately 20-50 fs.2,4,5 In terms of the afore-
mentioned classical description, Bersohn and Zewail62 have shown
that such “lifetimes" are related to the gradient dVx{r)/dr at the
central point of probing r = r* on the dissociative PES (corre-
sponding to maximum absorption of the probe pulse), and hence
to the velocity of fragment separation at r*. The deconvolved fit
to curve (v) of Figure 4 achieves maximum intensity at a time
/* «= 35 fs, corresponding to r* = 3.58 Á, where Vft) == 185 cm-1
(= = 191 cm-1, as expected62,63); it may be noted therefore that
even the most off-resonant probe-laser frequency employed2-5
interrogates the long-range tail of the reactive potential close to
the dissociation limit (Vx (r0) = £av = 6550 cm-1 for X, = 306 nm).
Figure 4 also shows a decreasing maximum signal intensity for
the five transients as the probe-laser frequency is successively
detuned to the red of the on-resonance wavelength, in agreement
with the findings of other workers.2-5,42-44,51,58-61 Williams and
Imre42 have invoked a curve-crossing mechanism, reminiscent of
the well-known Landau-Zener model, to explain such an obser-
vation: at higher probe-laser frequencies, commensurate with
long-time detection of [I—CN]4* at larger values of the reaction
coordinate (see Figure 1), the difference between the gradients
dy{(r)/dr and dK2(r)/dr of the two PESs connected by the
probe-laser pulse is less than at small values of r, thus enhancing
transfer of population to the upper potential V2{r) from V¡(r) and
giving rise to a more intense LIF signal. We find that maximum
LIF intensity is determined by convolution of the time-dependent
reaction dynamics with the temporal widths of the pump and probe
lasers: for -function pulses, the peak intensity is identical for
all transients, irrespective of probe-laser frequency, as has been
noted elsewhere;62,63 increasing the temporal pulse widths of the
two lasers up to fwhm = 125 fs both broadens and diminishes the
maximum peak intensity of the calculated signals, the effect of
which becomes more pronounced as the probe-laser frequency is
detuned from the long-time resonance value.2,4,5,7,11,62,63
B. Classical Simulations. Figure 5 depicts FTS spectra for
reaction la calculated from eqs 14 and 15 for the same laser
frequencies and pulse widths and model potential curves y¡(r)
and y2(r) as employed in the quantum-dynamical treatment of
the previous section. Comparison of Figures 4 and 5 reveals the
striking similarity between the quantum and classical calculations
of FTS data for reaction la. The on-resonance transient labeled
(i) in Figure 5 is characterized by a dissociation time of 1/2 =
44 fs, in reasonable accord with the value obtained from the
quantum-dynamical calculation (see below). From eq 11 we may
calculate that at a time t = 44 fs after impulsive bond cleavage,
(121) Dantus, M.; Janssen, . . M.; Zewail, A. H. To be published.
7982 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991
r/fs
Figure 5. Transient behavior calculated by classical mechanics. Graphs
of probe laser absorption A(r)/arbitrary units versus pump-probe time
delay r for a pump wavelength of ! = 306 nm and various probe
wavelengths X2. Times t* for input into eq 11 are calculated on the basis
of the distance traveled by a classical particle of reduced mass µ on K,(r)
so as to attain maximum absorption /4„,,(<*) at the different values of
X2: (i) t·
= 300.0
(s ®) fs (X2 = 388.5 nm); (ii) t* = 49.5 fs (X2 = 388.9
nm); (in) t* = 40.9 fs (X2 = 398.8 nm); (iv) t* = 38.2 fs (X2 = 390.4 nm);
(v) t* = 35.2 fs (X2 = 391.4 nm). Both laser pulses are transform-limited
Gaussians with fwhm = 125 fs (corresponding to spectral widths of fwhm
= = 118
cm"1), and values of A(r) are normalized with respect to the
long-time asymptote of the on-resonance signal (i). Parametrized forms
of K,(r) and K2(r) are those given in the caption to Figure 1. Note the
different long-time values of A(r) compared to <^2( )| 2( )> shown in
Figure 4 (see text for discussion).
the (classical) NC—I bond distance is r, = 3.8 Á. Further on-
resonance simulations carried out at initial energies £av corre-
sponding to X, = 295 and 285 nm excitation yielded transient
spectra characterized by dissociation times of r1(,2 = 41 and 39
fs, respectively.
That the classically determined values of are shorter than
those arising from the quantum-dynamical model of the preceding
subsection by some 15 fs may be considered to result from the
spreading of | ,( )) during its preparation on the excited-state
potential; we note that for X, = 306 nm and fwhm = 125 fs as
before, (r) = 3.2 and 6.7 Á at the temporal midpoint ( = 0 fs)
and end (r = 150 fs) of the pump-laser pulse, respectively, whereas
r0
-
2.89 A marks the initial coordinate of a classical trajectory
at the turning point of V¡(r) following Franck-Condon (vertical)
absorption from the extended ground-state species by means of
a -function laser pulse.
It may be noted that the asymptotic values of ( 2( )| 2(/))
displayed in Figure 4 pertaining to off-resonance probe-laser
frequencies (0.9349, 0.4789, 0.2111, and 0.0265 for the curves
labeled (ii)—(v), respectively) are larger than the corresponding
data for A{t) shown in Figure 5 (0.8741, 0.2293, 0.0445, and
0.0007 for the transients denoted (ii)-(v)). As pointed out in
section II.D, this simply reflects the squared dependence of /2(i>2)
on E^fa): the differences between the long-time signals calculated
by quantum dynamics and classical mechanics at a given
probe-laser frequency are consistent with a spectral half-width
for the electric vector E2(v2) (given by the asymptotes of
(MOWiU))) of the probe laser that is a factor of V2 higher than
that for the corresponding frequency distribution of the probe-
pulse intensity I2(J»2) (determined by the long-time values of A(t)).
The different asymptotic values of the graphs of Figures 4 and
5 naturally have an effect on the overall shapes of the calculated
FTS transients (so that, for instance, the maxima of the off-
resonance transients of Figure 5 peak at earlier times than the
analogous data shown in Figure 4).
Figures 2,4, and 5 together therefore indicate that the long-time
(Z
> 50
fs) dynamics of ICN dissociation according to reaction
Roberts and Zewail
la can be treated satisfactorily by classical mechanics for the
particular choice of temporal laser intensity profiles and potential
functions Vfr) and V2(r) used here.62,63 This latter aspect is a
reflection of Ehrenfest’s theorem; for t > 50 fs the derivative
dK,(r)/dr of the potential function is negligible over the dimensions
of the wave packet |^t(z)>, implying that its time-evolution may
be adequately described by Newton’s Second Law.115 For reaction
la studied under the experimental conditions employed in the FTS
measurements,2"5 it does not appear unreasonable to conclude
therefore that the assumption of a one-to-one correspondence
between the frequency of the probe-laser light and the distance
apart of the separating photofragments represents an adequate
working approximation.
The similarity between FTS transients predicted by quantum
dynamics and classical mechanics reflects the fact that in this case
the intrinsic spreading of the wave packet |V'i(/)> created on the
reactive potential V^r) is negligible over the time scale for dis-
sociation, such that the observed FTS behavior closely mimics
the experimental response function (defined as the integral of the
pump-probe correlation function4). As noted elsewhere,4·5 the
use of laser pulses with temporal widths «= 100-150 fs prevents
an analysis of spreading of | ( )> on Vfr) in this instance; in-
vestigations of the predissociation of Nal by FTS, on the other
hand, which occurs over a longer (picosecond) time scale, permit
the spreading of [Na—I]4* wave packets to be clearly re-
solved.102·116·117 In section II.D it was pointed out that it is nec-
essary to invoke both the above assumptions for successful ap-
plication of the potential inversion method developed by Bernstein
and Zewail63 and utilized below for analysis of the present data.
C. Inversion to the PES. Inversion of data of the type portrayed
in Figures 4 and 5 to generate the radial potential Vfr) may be
carried out routinely using eqs 17 and 11 following deconvolution
of the transform-limited pump- and probe-laser pulses. This is
illustrated in Figure 6a,b, which displays selected data points
(chosen to be approximately equidistant along the abscissa)
representing the inverted potential obtained from simulated data
of the type depicted in Figures 4 and 5 superimposed upon the
potential function F,(/·) from which the FTS transients themselves
were constructed, shown as a solid curve. Application of eq 17
to the time-resolved data calculated by quantum dynamics of
course requires prior conversion of the frequency dependence of
the electric vector E2(F2) to the spectral intensity distribution I2(y2),
The (expected) agreement between the inverted potential and K,(/·)
given by eq 16 is sufficiently satisfactory in our view so as to render
curve fitting to the inverted data points unnecessary in this in-
stance; both the quantum and classical simulations of reaction
la yield FTS spectra from which the (same) functional form of
K,(r) may be readily recovered by using the method of section
II. D.
Figure 7 shows graphs of ( 2( )\ 2( ) against time delay for
different probe spectral bandwidths at a single central
wavelength X2 = 391.4 nm, and clearly illustrates the effect of
varying the width of the optically coupled region provided by probe
pulses of different temporal duration. In all cases, the frequency
spread of the pump laser was kept constant at 118 cm"1,
=
corresponding to a pulse width in the time domain of 125 fs fwhm.
Similar calculations were carried out for these values of ? at
probe-laser wavelengths X2 identical with those employed in section
III. A for probe pulses of fwhm = 125 fs temporal duration.
Application of the potential inversion procedure outlined in section
II.D to data generated with different probe-laser bandwidths yields
results identical with that displayed in Figure 6a.
As a conclusion to this section, we illustrate the reconstruction
of the dissociative potential energy curve from presently available
experimental FTS data on ICN photodissociation.2"6 Figure 8
displays experimental transients for reaction la obtained at five
different probe laser wavelengths. If we assume that |F'1(/·) -
K,(r*)| » |V2{r) V2(r*)| and employ eq 11 to convert from
-
interfragment separation r to dissociation time Z, eq 8 may be
readily rearranged to yield an expression for the temporal potential
K,(Z) in terms of the deconvolved FTS data /(Z;X2), the spectral
bandwidth of the probe laser and the value of F,(z) at t = t*. The
Femtosecond Real-Time Probing of Reactions
Figure 6. Inversion to PES of FTS transients calculated by quantum
dynamics and classical mechanics. Graphs of F,(r) against Í—CN sep-
aration r obtained by inversion of simulated FTS transients in the form
of plots of (a) ( 2( \ 2( ) as a function of delay time shown in Figure
4 and (b) A(t) as a function of delay time shown in Figure 5. The
points represent values of F,(r) determined by inverting FTS data at
selected values along the dissociation coordinate using eqs 14 and 15: (·,
O) X2 = 388.5 nm ( = 0 cm*1); (·, ) X2 = 388.9 nm ( = 26 cm"1);
( , ) X2 = 389.8 nm ( = 86 cm"1); (A, ) X2 = 390.4 nm ( = 125
cm"1); ( , ) X2 = 391.4 nm ( = 191 cm"1). The solid line represents
the functional form F,(/·) = F,° exp(-a¡) relative to the dissociation limit
0i, from which the transients shown in Figures 4 and 5 were calculated:
F,° = 2.061 X 1010 cm"1; a, = 5.1813 A"1.
result of considerations of this type carried out by Dantus et a!.5
is displayed in Figure 9, in which values of V,(t) determined from
transient (iii) of Figure 8 are shown as data points at selected
values of t, while the potential function V, (t) calculated from eqs
11 and 16 by assuming a Lorentzian distribution of probe-laser
frequencies5 is represented by a solid curve.
D. Sensitivity of Calculated FTS Data to the Parametrized PES.
In this section, we consider the sensitivity of calculated FTS
spectra, obtained from both classical mechanics and time-de-
pendent quantum dynamics, to variation of the input values of
o¡ij, V|j°, a2k and V2k° (j
=
a, b, c; k = a, b) in the parametrized
forms for F,(r) and V2(r) given by eq 16.
1. Variation of Shape of F,(r). For a given functional form
of V2(r), here assumed independent of reaction coordinate (a2 =
==
A'1), FTS transients were computed by the quantum and
classical procedures outlined in sections II. A and II.B for three
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7983
r/fs
Figure 7. Transient behavior calculated by quantum dynamics for dif-
ferent probe-laser pulse widths. Graphs of the probability density ( 2-
( )| 2(<) > versus pump-probe time delay as a function of the temporal
duration of the probe-laser pulse. Transient (ii) displayed here is identical
with transient (v) shown in Figure 4; values of ( 2( )\ 2( ) for all curves
are normalized with respect to the maximum peak intensity of transient
(ii). Parametrized forms of F,(r) and V2(r) are those given in the caption
to Figure 1. Nominal (central) wavelengths are X, = 306 nm and X2 =
391.4 nm in all cases. Both pump- and probe-laser pulses are Gaussian
in shape; for the pump laser, the pulse width is fixed at fwhm = 125 fs
(AP = 118 cm"1). Probe pulse durations and spectral bandwidths are (i)
fwhm = 259 fs (AP =59 cm"1), (ii) fwhm = 125 fs (AP = 118 cm"1), (iii)
fwhm = 62.5 fs ( > = 236 cm"1), and (iv) fwhm = 12.5 fs (AP =1180
cm"1).
TABLE I: Parameters Characterizing Different Potential Functions
F„(r), Given by V,j(r) = F,,e exp(-«,jr) with j = a, b, or c,
Employed To Investigate FTS Behavior for Different Exponential
Forms of the Dissociative Potential (V¡(r) = ß2 0¡ = 24630 cm"1)
-
_«ii/ "1_FijVcm"1_ 2.0610 X 1010
V¡,(r) 5.1813
Klb(r) 1.2500 2.4272 X 10s
Vlc(r) 21.4767 5.6239 X 1030
dissociative potentials F^r) (j = a, b, c), all of the general form
given by eq 16. The various parameters an and F,j° employed
to construct the different Vv¡(r) are listed in Table I, while Figure
10 illustrates the resulting potential curves. Fla(r) is identical
with that employed in the calculations reported in sections III. A
and III.B and comprises the parameters for the excited dissociative
state of ICN leading to ground-state (CN(X2S+) + I(2P?/2)
photofragments selected by Bersohn and Zewail62 (see section
II.C). The value of alb is that derived by Dantus et al.3"5 from
investigations of the dissociation time of reaction la by FTS (see
section III.A), while alc was chosen to be greater than ala by a
factor identical to that by which alb is smaller than ala. Flb° and
Flc° were determined such that the classical turning points of the
three PESs occurred at the same I-CN separation r0 = 2.89 A
for initial wave packet preparation at an energy £av above 0, (using
X,
= 306 nm
pump radiation). For all three potential functions
Fjj(r) therefore, the wave packet initially created on the excit-
ed-state surface by the pump laser will achieve asymptotically the
same group velocity, although of course the acceleration of the
packets will differ in each case.
Figure 1 la,b shows time-dependent LIF signals calculated by
quantum dynamics and classical mechanics, respectively, for the
potential energy curve designated Flb(r); transients obtained for
the potential Flc(r) are likewise displayed in Figure 12a,b.
Analogous data for F,a(/·) have been presented previously as
Figures 4 and 5. A number of points bear comparison with regard
to the FTS transients presented in these diagrams. First, it may
be noted that the transients calculated by classical mechanics
resemble qualitatively those obtained from the full quantal
7984 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 Roberts and Zewail

e
s

a
c
M

E
o
n
O
r/fs
Figure 8. Experimental transient behavior of ICN dissociation. Graphs
\
Ed
of LIF signal intensity (arbitrary units) versus pump-probe time delay
r recorded at a pump wavelength of X, = 306 nm and various probe
wavelengths (X2, nm): (i) 388.5; (ii) 388.9; (iii) 389.8; (iv) 390.4; (v)
391.4. Observed intensities are normalized with respect to the long-time
asymptote of the on-resonance transient (i). The solid line through each
set of data points represents the result of an optimized fit according to
the classical model of section II.B convolved with the Lorentzian profile
of the measured cross correlation of the pump- and probe-laser pulses
(adapted from ref 5).

Figure 10. Potential energy curves relevant to examination of the vari-

Figure 9. Comparison of PES with result derived from FTS experiments.
Graph of Vx(t) against classical dissociation time t obtained from ex-
perimental FTS data. The points represent values of K,(f) as selected
values of t determined from transient (iii) of Figure 8 (X2 = 389.8 nm
( = 86 cm"1)) following deconvolution of the experimental response
function and assuming a Lorentzian profile for probe-pulse absorption
with fwhm * 204 cm'1. The solid line represents the potential function
K|(r) = £,, sech2 (ctax/2) derived from eqs 13 and 15 with the value a,
= 1.1905 A"1 obtained from the optimized fit through the observed data
shown as Figure 8(iii) (adapted from ref 5).
treatment, with best quantitative agreement obtained for the
ation of FTS signal intensities with modification of the shape of Vx(r).
Diagrams of excited-state potential functions relative to dissociation limit
ß , illustrating the different Vx¡(r) employed to determine the effect of
variation in shape of the reactive potential on calculated FTS data (shown
in Figures 11 and 12). Potential parameters are taken from Table I.
pulse occurs at increasingly large I—CN distances; in terms of
the classical mechanical description of section II.B, r* and t*
increase with decreasing ay for a given off-resonance probe
wavelength.
The dissociation time t1/2 for the on-resonance signals of Figures
11 and 12 also reflect the different gradients dKy(r)/dr over those

potential function Vx¡(r) = Klb(r) that is constructed from the
smallest value of «y (see below). As may be readily anticipated,
it is found that as the value of ay is decreased (i.e„ as the potential
curve becomes less sharply repulsive), the maximum LIF intensity
for a probe-laser pulse of given wavelength X2 shifts to longer delay
times (compare especially Figure 11 with Figures 4 and 12),
indicating that the region of Vx¡(r) sampled by the probe-laser
regions of r where Vx¡(r) changes significantly. The three on-
resonance transients calculated by perturbation theory, denoted
(i) in Figures 4, 11a, and 12a, are characterized by values of µ
60, 185, and 25 fs; the corresponding classical data, shown in
Figures 5, lib, and 12b, give rise to dissociation times of 1/2 =
44, 181, and 11 fs. As alluded to above in general terms, it may
be noted that the closest agreement between quantum and clas-
Femtosecond Real-Time Probing of Reactions
Figure 11. Transient behavior calculated by quantum dynamics and
classical mechanics for the set of potential functions shown in Figure 10b.
(a) Graphs of ( 2(/)| 2(0) versus pump-probe time delay for a pump
wavelength of , = 306 nm and various probe wavelengths ( 2, nm): (i)
388.5; (ii) 388.9; (iii) 389.8; (iv) 390.4; (v) 391.4. (b) Graphs of
probe-laser absorption A(t)/arbitrary units versus pump-probe time
delay for a pump wavelength of , = 306 nm and various probe
wavelengths 2. Times t* for input into eq 11 are (i) t* = 500.0 (= =)
fs ( 2 = 388.5 nm), (ii) /* = 205.1 fs ( 2 = 388.9 nm), (iii) t* = 169.5
fs (X2 = 398.8 nm), (iv) r* = 158.3 fs (X2 = 390.4 nm), and (v) t* =
145.6 fs (X2 = 391.4 nm). Both pump- and probe-laser pulses have
Gaussian temporal profiles of fwhm = 125 fs (corresponding to spectral
widths of fwhm = = 118 cm'1 for transform-limited pulses), and
values of ( 2( )|^2(/)> and A(t) are normalized with respect to the
long-time asymptote of the on-resonance signals labeled (i).
sically calculated values of rw2 is achieved for the dissociative
potential Klb(r) with the smallest value of a,j, since in this case
the (long-time) dynamics of the wave packet prepared on the
excited-state potential will most closely resemble the motion of
a classical particle. (From an alternative perspective, the distance
traveled by a classical particle within a time period t = t1/2 is
significantly greater than 1 /ay¡, an assumption required for de-
rivation of eq 18 below.)
This variation of ti/2 may be placed on a more quantitative basis
by means of the classical expression
T./2
=
(l/«,jy) In [8£8 / ] (18)
previously obtained by Rosker et al.,4 which relates the dissociation
(or clocking) time t1/2 to the length parameter \/aVi of the ex-
ponential PES Vifr). As noted in section III.A, t1/2 represents
the time taken by a classical trajectory starting from initial co-
ordinate r0 on the potential energy curve Vfr) to arrive at that
position within the detection window defined by an on-resonance
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7985
N
%
%
v
W
4->
3
3
X>
a
t-
r/fs
Figure 12. Transient behavior calculated by quantum dynamics and
classical mechanics for the set of potential functions shown in Figure 10c.
(a) Graphs of ( 2( )| 2(0) versus pump-probe time delay r for a pump
wavelength of X, = 306 nm and various probe wavelengths (X2, nm): (i)
388.5; (ii) 388.9; (iii) 389.8; (iv) 390.4; (v) 391.4. (b) Graphs of probe
laser absorption A(f)jarbitrary units versus pump-probe time delay r
for a pump wavelength of X, = 306 nm and various probe wavelengths
X2. Times t* for input into eq 11 are (i) t*
= 300.0
(= =>) fs (X2 = 388.5
nm), (ii) t* = 11.9 fs (X2 = 388.9 nm), (iii) t* = 9.9 fs (X2 = 389.8 nm),
(iv) t* = 9.2 fs (X2 = 390.4 nm), and (v) r* = 8.5 fs (X2 = 391.4 nm).
Both pump- and probe-laser pulses have Gaussian temporal profiles of
fwhm = 125 fs (corresponding to spectral widths of fwhm = = 118
cm"1 for transform-limited pulses), and values of (^MI^M) and A(t)
are normalized with respect to the long-time asymptote of the on-reso-
nance signals labeled (i).
probe-laser pulse where Kj(r) = /2 cm"1. (From an experi-
mental point of view, t1/2 is measured as the time at which the
on-resonance fluorescence signal attains 50% of its long-time
intensity.)3"5·7·8·11 From the t1/2 values reported above for transients
calculated by classical mechanics, values of ay¡ = 5.14,1.25, and
20.57 Á'1 for j = a, b and c may be recovered, in overall agreement
with the input parameters listed in Table I.
The off-resonance transients of Figure 1 la,b (labeled (ii)-(v),
as before), when deconvolved from the temporal response of the
combined effect of the pump- and probe-laser pulses, indicate that
[I—CN]** species persist for times of the order of 18-52 fs
measured at fwhm of the deconvolved signals; such lifetimes are
in good agreement with the experimentally derived values2·4·5 (see
section III.A). In contrast, [I—CN]** transition states propagating
along the potential curve Kl0(r), giving rise to the transient be-
havior shown in Figure 12, are found to lead an extremely eva-
nescent existence, lasting for durations less than approximately
6 fs as the dissociating intermediates traverse the fwhm of the
7986 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991
Figure 13. Inversion to PES of FTS transients calculated by quantum
dynamics for the dissociative potentials KIb(r) and K)c(r). Graphs of
Fij(r) against I—CN separation r obtained by inversion of simulated FTS
transients in the form of plots of <^2( ) 2(0> versus delay time r. (a)
F|j (r)
=
Klb(r); (b) Ky(r) = K,c(r). The points represent values of V¡fr)
determined by inverting the FTS data shown in Figures 11a and 12a at
selected values along the dissociation coordinate using eqs 14 and 15: (·)
2 = 388.5 nm ( = 0 cm'1); (·) X2 = 388.9 nm ( = 26 cm"1); ( ) X2
= 389.8 nm ( = 86 cm"1); ( ) X2 = 390.4 nm ( = 125 cm"1); ( )
X2
= 391.4 nm
( = 191 cm"1). The solid line represents the functional
form VvXr) = Ky° exp(-ay) relative to the dissociation limit 0,, from
which the transients shown in Figures 1 la and 12a were calculated.
probe-laser frequency spectrum en route to asymptotic product
states. Once again, the longer lifetimes enjoyed by [I—CN]**
in the former case simply reflects the shallower gradient of the
potential Klb(r) compared to Klc(r). The group velocity of the
wave packet monitored by the laser pulse (dr(i)/dt = v[l
FytO/E,,,,]1/2 in the classical mechanical description, where v is
the terminal recoil velocity) at a particular wavelength X2 is
identical in both cases, even though (r> (r*) is different, so that
the evolving system samples transition-state configurations for
a longer period of time at larger I—CN distances when ay is
smallest; i.e., for a given off-resonance probe wavelength, the
second laser pulse spans a larger optically coupled region con-
necting the two surfaces Ky(r) and V2(r) for smaller values of
ay.
Inversion of the FTS transients calculated by quantum dynamics
shown in Figures 11a and 12a in a manner analogous to that
carried out in section III.A for Kla(r) yields the results displayed
in Figure 13, which shows as usual the inverted data points su-
perimposed upon the potential functions V¡b(r) and Klc(r) from
which the FTS signals were originally constructed. The same
Roberts and Zewail
.5 _i_I_i_I_i_I_i I ' I ' I
2 3 4 5 6 7 8
r/A
Figure 14. Potential energy curves relevant to examination of the vari-
ation of FTS signal intensities with modification of the shape of V2(r).
Diagrams of excited-state potential functions relative to dissociation limit
0i, illustrating the different K^f/·) employed to determine the effect of
variation in shape of the second-excited potential on calculated FTS data
(shown in Figures 15 and 16). Potential parameters are taken from Table
II.
procedure was also carried out for the classical results of Figures
1 lb and 12b, from which Klb(r) and Klc(r) were similarly obtained.
That different probe-laser frequencies span the largest range of
interfragment separations and are shifted to larger r values for
the smallest value of ay (= a,b) is clearly illustrated by comparison
of Figure 13a with Figures 13b and 6; for Klc(r) for example, it
is only possible to recover the potential function over a range of
I—CN distances approximately some 0.5 Á wide. In all cases,
however, the probe-laser pulse samples the long-range part of the
-
dissociative potential. In addition, the more widely separated
deconvolved FTS data (in terms of the times at which maximum
signal is achieved at different probe wavelengths) obtained for
K,b(r) permit a more precise determination of the potential than
is possible for more steeply repulsive curves for which the peak
intensities of the resulting transients are bunched closely together
at short(er) times. Finally, Figures 6 and 13 clearly illustrate the
point made by Bernstein and Zewail63 concerning the redundancy
in the deduced Ky(r) data obtained from eq 17, which relies upon
the spectral width of the probe-laser pulse. For the probe fre-
quencies used here, broadly overlapping values of Ky(r) can be
determined in each case, though of course, the longest wavelength
X2 extends the range of Ky(r) values to shorter interfragment
distances.
2. Variation of Shape of V2(r). A study of the effects on the
calculated FTS transients obtained by varying the nature of the
 Femtosecond Real-Time Probing of Reactions The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7987

TABLE II: Parameters Characterizing Different Potential Functions

Vjk(r), Given by Va(r) = Va# exp(-ear) + (0, 0,) with k = a
-

or b, Employed To Investigate FTS Behavior for Different

Exponential Forms of the Potential Accessed by the Probe· Laser
(V,(r) Flt(r) 2.4272 X 10*
Pulse = =
exp(-1.2S00i·))_
_«a/A"'_ty/cm'1 (0: -

dil/cnr1
V^r) co 24630
y2i(r) 1.2798 2.5653 X 10s 24630

uppermost PES V2(r) accessed by the probe-laser pulse has also

been carried out. Figure 14 shows the two sets of excited-state
potential energy curves V,(r) and K2k(r) (k = a, b) employed in
this aspect of our investigations; V2a(r) displayed in Figure 14a
is independent of reaction coordinate as before, while Figure 14b
illustrates an exponentially repulsive form K2b(r). Table II lists
the various parameters a2k and V2k° used to construct the two
potential functions K2k(r). Vfr) here is the same as Flb(r) of the
preceding section, the parameters for which are given in Table
I.
The transient behavior resulting from the potential curves il-
lustrated in Figure 14b (i.e., for exponentially repulsive K2b(r))
is displayed in Figure 15a,b, which shows FTS signals calculated
by means of the quantum and classical treatments of sections II.A
and II.B, respectively. In the case where the second-excited
potential is independent of dissociation coordinate (K2a(r) = 02
-

0|), analogous data are displayed in Figure 11. Comparison

of either Figures 11 a and 15a or Figures 11 b and 15b reveals the
consequences of adding a repulsive term to the upper excited
potential energy curve; as K2k(r) is made increasingly repulsive
(i.e., as a2 of eq 16 is decreased from = <=° A"1
corresponding
to a linear potential curve to a finite value of the order of a2b«
alb), a probe laser pulse of given off-resonance frequency samples
regions of the reactive potential Klb(r) at ever decreasing inter-
fragment separations, and hence also time delays; otherwise the
shapes of the calculated FTS transients are broadly similar in
shape for both potential energy curves K2k(r). Again, in the
language of the classical model presented in section II.B, for a
given off-resonance probe-laser wavelength, r* and t* decrease
in value as the range parameter a2k is reduced.
The dissociation times that characterize the two on-resonant
FTS spectra depicted in Figure 15a,b are 1/2 = 88 and 74 fs,
respectively, considerably smaller than the results obtained for
Vtoir), where values of r, ,2 = 185 and 181 fs were obtained from
the quantum and classical treatments. When a2k = a2b °°
A'1,
eq 12 does not readily lend itself to development of a classical
expression for xl/2 in the same way that eq 14 leads to eq 18 in
the limit that t -* =; nevertheless, the much smaller values of r,/2
determined in this case are consistent with a simple picture
(namely the detection window62·63) in which the dissociative po-
tential is probed by means of a vertical transition of wavelength
2 that connects Vfr) and V2k(r) at ever shorter interfragment
distances along the reaction coordinate as K2k(r) becomes in-
creasingly repulsive.
Deconvolution of the off-resonance transients shown in Figure
15 from the cross correlation of pump- and probe-laser pulses
permits estimation of transition-state lifetimes for [I--CN]**
measured at fwhm of approximately 50-70 fs. That these times
are longer than the values between 18 and 52 fs reported above
for V^r) is a manifestation of the dual effects of the larger
optically coupled region at shorter internuclear separations gen-
erated by the probe laser when K2b(r) is no longer independent
t/fs
Figure 15. Transient behavior calculated by quantum dynamics and
classical mechanics for the set of potential functions shown in Figure 14b.
(a) Graphs of (^2(f)|^2(f)> versus pump-probe time delay for a pump
wavelength of , = 306 nm and various probe wavelengths (X2, nm): (i)
388.5; (ii) 388.9; (iii) 389.8; (iv) 390.4; (v) 391.4. (b) Graphs of
probe-laser absorption /4(x)/arbitrary units versus pump-probe time
delay x for a pump wavelength of X, = 306 nm and various probe
wavelengths X2. Times t* for input into eq 11 are (i) t* = 500.0 (= ®)
fs (X2 = 388.5 nm), (ii) t* = 137.0 fs (X2 = 388.9 nm), (iii) t* = 86.6
fs (X2 = 389.8 nm), (iv) t* = 65.8 fs (X2 = 390.4 nm), and (v) t* = 22.5
fs ( 2 = 391.4 nm). Both pump- and probe-laser pulses have Gaussian
temporal profiles of fwhm = 125 fs (corresponding to spectral widths of
fwhm = = 118 cm"1 for transform-limited pulses), and values of
IlMOIlMO) and A(t) are normalized with respect to the long-time
asymptote of the on-resonance signals labeled (i).
shown as a solid line upon which are plotted the inverted data
points derived from the FTS transients themselves. In the case
when the second-excited potential V2(f) (= V^r)) is independent
of reaction coordinate, the result of inverting to the potential
function K)b(r) has been presented earlier as Figure 13a. Owing
to the broad spectral width of the probe-laser pulse in relation
to the maximum detuning increment =
?2“ P2 = 191 cm-1
-

of reaction coordinate and the smaller local group velocity of the
accelerating wave packet (v(t) for a classical particle) interrogated
at shorter average distances (r) (r* or t* corresponding to
maximum absorption of a probe pulse of given frequency).
employed in this study, each of the transients shown in Figure
15 generates an essentially identical data set of | 21(/·)| values
irrespective of probe-laser wavelength (we note that the maximum
value of | 2 (/·)|, attained at r = l/(alb a2b) In (cc,bKlb0/
-

Figure 16 displays the results of carrying out inversion to the
potential F|b(r) by means of the procedure outlined in section II.D
on the calculated FTS data presented in Figure 15. In contrast
to previous examples of the method given earlier in this paper,
application of eq 17 in this case generates a difference in potentials
|AF21(r)| = \Vlh{r) Klb(r)|, as pointed out in section II.D; in the
-
“2bF2b°) » 2.6 A, is only about 206 cm"1): for presentation
purposes, we have chosen to illustrate in Figure 16 the results of
applying eq 17 to the calculated quantum and classical data
obtained for X2 = 389.8 nm, corresponding to a detuning increment
of = 86 cm"1 with respect to the on-resonance probe wavelength
X2“ = 388.5 nm. For the same reason, a broadly similar range

standard manner adopted throughout this paper, this function is of coordinate positions along Flb(r) can be interrogated for both
7988 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991
Figure 16. Inversion to potential difference of FTS transients calculated
by quantum dynamics and classical mechanics, (a) Graph of |AF21(r)|
against reaction coordinate r obtained by inversion of FTS data simulated
by quantum dynamics, (b) Graph of | 21(/)| against classical disso-
ciation time t obtained by inversion of FTS data simulated by classical
mechanics. The points represent values of | 2,(/·)| and | 2 ( )| at
selected values of r and t determined by inverting the transients labeled
(iii) of Figure 15a,b using eqs 14 and 15: 2 = 398.8 nm ( = 86 cm'1).
The solid curves shown in both graphs represent the functional forms
| 21( )| = |/l>y*)| and |AF21(f)| = [/(r,f*)| given by eq 13, from which
transients (iii) of Figure 15a,b were calculated.
pairs of potentials Flb(r)/F2a(r) and F]b(r)/F2b(r) even though
the times t* and distances r* for maximum absorption of the probe
pulse at a given frequency are shifted to smaller values in the latter
case. (For example, for = 86 cm'1: t* = 169 fs and r* = 6.4
A when F2k(r) = F2a(r); f* = 87 fs and r* = 4.2 A when F2k(/·)
=
F2b(r).)
Figure 16a displays the result of inverting to the potential
difference |AF21(r)| from the calculated time-dependent FTS signal
labeled (iii) in Figure 15a, where the known function | 21(/·)|
is plotted against dissociation coordinate as before. The result
of inverting the corresponding classical data of Figure 15b is shown
in Figure 16b, in which by way of contrast |AF21(r)| is recast as
a function of the time t that measures the evolution of a classical
trajectory over Flb(r) to give |AF2l(f)| (see section II.B). Values
of | 21( )| and | 2,( )| obtained from FTS data displayed in
both Figures 16a and 16b are identical, however. We note that
the inversion procedure of Bernstein and Zewail63 requires that
| 2,(0| be related to the observed FTS signal by an expression
of the form ( ; 2) = Cexpf- (In 2)[F2(t) F,(Z) + ]2/( >/2)2};
-
comparison with eq 12 indicates that |AF21(f)| may therefore be
Roberts and Zewail
equated with/V,i*) (and |AF21(r)| wither/*)), i.e. that/(<>**)
=
±( /2)[1 2]1''2 (see eq 17). Since the method
[C/Z(í;X2)]/ln
of carrying out the inversion to |AF21(r)| embodied by eq 17 is
strictly a classical procedure, it is not possible to obtain values
of 2 (/·)| from the FTS transients themselves at interfragment
distances smaller than r0 = 2.89 A, the initial coordinate (cor-
responding to t = 0) for classical absorption of pump-laser light
at Xt = 306 nm by ground-state ICN to the excited-state potential
The results of subsections III.D.l and III.D.2 show that changes
to parameters in the exponential expressions for the potentials
Vyfr) and F2k(r) can result in considerable variation in the time
dependence of calculated FTS spectra. It is clear that clocking
of a direct photodissociation reaction in FTS experiments (i.e.,
determination of t1/2 using probe-laser light that is on resonance
with a free-fragment transition) is sensitive to the shape of both
excited-state potential energy curves.
E. Centrifugal Effects on Calculated FTS Data. Inclusion of
an additional term in the dissociative PES V, (r) describing the
centrifugal barrier122 to reaction might be expected to give rise
to dynamical effects that manifest themselves in the time domain
in such a way as to be readily discernible from FTS spectra. In
order to assess the possibilities from the classical perspective of
section II.C, a preliminary analysis of the variation of probe-pulse
absorption along the reaction coordinate has been carried out for
ICN dissociation via the less energetic reaction channel la leading
to ground-state CN(X22+) + I(2P3/2) products.
To take account of the centrifugal effect in the potential function
controlling reaction, eq 16 is recast in the form122
V,'n(r) =
Vfr) + /(/ + l)h2/2ur2 (19)
where l is the quantum number corresponding to the orbital
angular momentum L of relative motion during the half-collision,
and the radial or central potential term F,(r) = F,° exp(-a,r)
+ ft, as before. Figure 17a,b display two potential energy curves
F,eff(z·) relative to the dissociation limit 0 for values of the
=
orbital angular momentum quantum number / = 50 and 200. In
each case F^r) =
F,(r) for / = 0 is shown for comparison, as
is the centrifugal term /(/ + \) 2/2µ/2. The parameters F,° and
a, required for calculation of Vt{r) according to eq 16 are those
employed in section II.D for F,(r) = Flb(r); i.e., F,° = Flb° =
2.4272 X 105 cm'1 and a, = alb = 1.2500 A'1. Immediate in-
spection of these two diagrams reveals how the PES is shifted to
longer distances along the radial direction with increasing cen-
trifugal force.
For the different potential energy curves depicted in Figure 17,
the dependence of probe-pulse absorption A(r) on the distance
apart of the recoiling photofragments has been calculated using
eq 8. The pump-laser wavelength is fixed at X, = 306 nm in all
cases, giving rise to different initial coordinates r0 for classical
motion over each of the potential energy curves. Displayed in
Figure 18 are the resulting graphs of absorption A(r) versus
interfragment distance for the same on-resonance frequency and
four off-resonance frequencies employed throughout section III.
It should be pointed out that since these data are not displayed
in the time domain, convolution of the dynamics with the finite
temporal widths of the pump- and probe-laser pulses has not been
taken into account: the graphs of Figure 18 represent “deconvolved
transients” of probe-laser absorption as a function of I—CN
separation. A forthcoming publication123 will include integration
of the classical equations of motion for reaction over PESs of the
form given by eq 19 in order to predict the expected FTS behavior
as a function of time and thus to offer a more valid comparison
with experiment. Nevertheless, some interesting points do emerge
from the preliminary analysis carried out so far.
When centrifugal effects are neglected, the resulting absorption
A(r) as a function of radial distance r corresponds exactly to that
(122) Levine, R. D.; Bernstein, R. B. Molecular Reaction Dynamics and
Chemical Reactivity, Oxford University Press: New York, 1987; Chapter 2,
pp 43, 44, 58.
(123) Roberts, G.; Zewail, A. H. To be published.
Femtosecond Real-Time Probing of Reactions The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7989

tzi
+J

t*
<d

t-.

Figure 17. Effective potential energy curves consisting of a central po-

tential and centrifugal barrier. Diagrams of the excited-state potential
function Kieff(r) (—) relative to dissociation limit showing the inclu-
sion of a centrifugal barrier term /(/ + 1) 2/2µ 2 (-·-) relative to the
radial potential K,(r) (—) for different values of the orbital angular
momentum quantum number /: (a) I = 50; (b) / = 200.

expected from the temporal absorption A(t) discussed previously

in section III.B. Figure 18a shows plots of A(r) versus reaction
coordinate for zero orbital angular momentum; when transformed
into the time domain using eq 11 and convolved with the temporal
widths of Gaussian-shaped pump- and probe-laser pulses of fwhm
= 125 fs using eq 15, these data yield FTS spectra that are
identical with those displayed in Figure 5.
Presented in Figure 18b,c are analogous graphs of probe-pulse
absorption versus interfragment separation for values of / = 50
and 200, respectively. Comparison of any two plots displayed in
these figures for a given probe-laser wavelength, together with
the corresponding data shown in Figure 18a, reveals that as orbital
angular momentum / is increased, the onset of absorption com-
mences at larger values of interfragment separation (and hence
longer delay times), as may be anticipated from the form of the
potential energy curves shown in Figure 17. At a given photolysis
wavelength therefore, the dissociation times t¡/2 resulting from
the on-resonance curves denoted (i) in Figure 18 would accordingly
be expected to increase as the centrifugal contribution becomes
larger. Similarly, the delay times at which the off-resonance curves
labeled (ii)-(v) attain maximum intensity would also be expected
to increase as orbital angular momentum is increased. Figure 18
further indicates that the peak widths of off-resonance data become
correspondingly broader as the centrifugal effect becomes in-
creasingly predominant. This too is readily explainable in terms
Figure 18. Coordinate-dependent probe-laser absorption predicted for
dissociation over the effective potential functions displayed in Figure 17.
Graphs of probe-laser absorption /4(r)/arbitrary units as a function of
1—CN separation r along the dissociation coordinate of the potential
energy curves shown in Figure 17 for a pump wavelength of [ = 306
nm and various probe wavelengths ( 2, nm): (i) 388.5; (ii) 388.9; (iii)
389.8; (iv) 390.4; (v) 391.4. Distances r* (A) for input into eq 8 are as
follows, (a) / = 0 ( ,' ) = F,(r)): (i) 15.250 (= =); (ii) 7.315; (iii)
6.355; (iv) 6.055; (v) 5.720. (b) l = 50: (i) 40.000 (= »); (ii) 9.200; (iii)
6.890; (iv) 6.445; (v) 5.990. (c) l = 200; (i) 40.000 (= «·); (ii) 34.745;
(iii) 19.105; (iv) 15.845; (v) 12.820. The probe-laser pulse is Gaussian
of spectral width > (fwhm) = 118 cm"1 (corresponding to a temporal
profile of fwhm = 125 fs for transform-limited pulses).
of the potential energy curves displayed in Figure 17: as the
centrifugal term of eq 19 is increased, the repulsive short-range
part of the potential K,eff(/·) becomes less severe—that is to say,
7990 The Journal of Physical Chemistry, Vol. 95, No, 21, ¡991
the decrease in potential energy to the dissociation limit extends
over a larger distance as orbital angular momentum is
increased—with the result that the absorption A(r) extends over
a larger range of coordinate positions for a probe-laser pulse of
given spectral width .
As a broad conclusion to the initial study of centrifugal effects
on the reactive potential presented via Figure 18, it may noted
that FTS measurements of the real-time dynamics of dissociation
reactions afford the opportunity of elucidating the effective po-
tential V{t{t(r) from measurements of the dissociation times as-
sociated with final product formation and the lifetimes of tran-
sition-state configurations, etc. Such experiments should further
permit the separation of the centrifugal term, thus enabling the
form of the resultant radial potential K,(r) to be ascertained,
provided that the orbital angular momentum associated with a
given half-collision process can be determined. For dissociation
of ICN according to reaction 1, this can be achieved5"7 by mon-
itoring production of CN radicals in specific rotational states
(though the broad spectral bandwidth of femtosecond pulses in
effect means that only a distribution of closely-spaced rotational
levels can be probed at a given frequency), which may be identified
with the orbital angular momentum of the reaction as outlined
below.
Comparison of the CN rotational-state distributions of reactions
la and lb determined by experiments carried out with a supersonic
molecular beam source,19·20,27 characterized by a rotational tem-
perature for ICN of a few kelvins, with analogous room-tem-
perature measurements where the parent molecule is in thermal
equilibrium,12'20·26·29·31·32 indicate that initial parent rotation is of
relatively minor importance in determining the subsequent dis-
sociation dynamics that lead to substantial rotational excitation
of the CN photoproduct of reaction la.17,39·47·52·53·56·57 Following
the line of reasoning presented by Hall et al.,26 it is assumed that
the initial rotational angular momentum JICN of the parent species
is zero before the half-collision (i.e., that ICN resides solely in
its ground rotational level). Conservation of angular momentum
during the reactive process requires that
Jicn = 0 = L + Jcn + Ji (20)
where L denotes the orbital angular momentum of the half-col-
lision, JCn = N ± 1/2 is the total angular momentum of the CN
radical (excluding nuclear spin) and J! = 3/2 or 1 /2 represents
the total angular momentum of the I-atom fragment. For large
values of N, the approximation JCn = N and JCn, L » J| can be
made,26 in which case eq 20 collapses to the simple equality
L = -N (21)
The vector describing rotational angular momentum of the CN
product is therefore equal in magnitude but opposite in direction
to that of the orbital angular momentum of relative motion during
the dissociation. Measurements of the CN product in different
rotational quantum states thus constitute a direct handle on the
orbital angular momentum of the half-collision via the equality
(21) and, since /(/ + l)1/,2ft = fwb,m the impact parameter b also.
Following ICN excitation at , = 306 nm (where only
ground-state I(2P3/2) atoms can be produced) and 285 nm (where
both exit channels (la) and (lb) are energetically accessible),
Dantus et al.5 have determined dissociation times t,/2 for reaction
1 over a range of probe-laser wavelengths, corresponding to
formation of CN radicals in different rotational states. Probing
at the P-branch band head of the (0,0) band of the CN 2 +
2 + transition at 2 = 388.5 nm, where CN in rotational
quantum levels N = 25 is monitored, these workers obtained
dissociation times in the ranges 1/2 = 175-205 and 145-160 fs
for pump wavelengths of X, = 306 and 285 nm, respectively (with
a standard error of about 30 fs associated with each measurement);
near the onset of the P-branch lines at X2 = 387.5 nm, however,
commensurate with lower product rotational energies (JV < 5),
values of r,/2 that were much shorter than those for N » 25 were
determined.5 Qualitatively therefore, it may be noted that the
variation of dissociation time with product rotational state is
consistent with the discussion presented above, though the observed
Roberts and Zewail
increase in r1/2 with rotational energy is remarkably large for a
change in orbital angular momentum quantum number from /
5 to 25. It is stressed that a detailed quantitative appraisal
of these data, together with the elucidation of K,cff(r) and F3(r)
by means of 19, has yet to be carried out and awaits the completion
of our classical calculations.123 As noted in section I, Zewail has
previously considered the variation of r1/i2 with probe-laser fre-
quency in terms of initial bending motion of the ICN precursor
and subsequent motion of [I—CN]** intermediates over an an-
gle-dependent PES, in addition to possible centrifugal effects.7
IV. Dissociation of Bi2: Application to a Heavy-Particle
System
In order to test the theoretical approaches of section II on a
system of kinematic characteristics grossly dissimilar to that of
reaction 1, both quantum dynamical and classical treatments
described therein have recently75 been applied to the ultraviolet
photofragmentation of diatomic bismuth, which is also considered
to proceed over PESs that are repulsive in character at distances
greater than the Franck-Condon region.124 Following absorption
of a femtosecond laser pulse at Xt = 308 nm, the dissociation
reaction results in production of ground-state Bi(4S03yi2) atoms and
the two spin-orbit components of the first-excited 2D°y term:
2( ' +8) [Bi-Bi]** Bi(6p3 4S°3/2) + Bi(6p3 2D°3/2)
— -
(22a)
[Bi-Bi]** Bi(6p3 4S°3/2) + Bi(6p3 2D°5/2)
- -»
(22b)
The first subpicosecond real-time investigations of reaction 22 were
carried out by Sorokin and co-workers, who recorded broadband
frequency-resolved absorption spectra in the vicinity of atomic
resonance lines originating from the 2D°3z2 and 2D°5jz2 levels as
a function of pump-probe time delay t. 124-126 The results of their
investigations led these workers124 to propose an exponential de-
pendence on internuclear separation (of the form given by eq 16)
for two noninteracting potential energy curves V\(r) and Vy(r)
that govern the dynamics of reactions 22a and 22b.
Application of the FTS technique to the investigation of Bi2
dissociation has resulted in the acquisition of information about
the reaction dynamics over a range of internuclear coordinates
on the two PESs controlling reaction via both exit channels.75 In
contrast to the experimental scheme for probing the ICN disso-
ciation reaction illustrated in Figure 1, a probe-laser pulse of given
wavelength that monitors the evolution of reaction 22 can result
in the population of several closely-spaced high-lying PESs V2(r)
that correlate with high-lying electronic levels of atomic Bi. Owing
to the coincidence of the probe-laser frequency with energy sep-
arations within the electronic structure of Bi atoms and between
the perturbed levels of the [Bi-Bi]** moiety, it is therefore possible
to interrogate the dynamics of reactions 22a and 22b individually
at both final-product and transition-state configurations on the
dissociative PESs F,(r) and Vy(r) by monitoring the transient
behavior at different fluorescence wavelengths Xdet.75
To illustrate the nature of the data75 that can be obtained from
FTS measurements in this case, just two examples of experimental
transients that probe the dynamics of dissociating Bi2 molecules
over the lower-lying PES ,( ) leading to 4S°3y2 +
2D°y2 product
levels are displayed in Figure 19a. Further examples of FTS data
pertaining to this and the higher-lying exit channel (22b), together
with details of their interpretation, are given in the recent pub-
lication of Bowman et al.75 Both transients shown in Figure 19a
were recorded at a single probe wavelength of X2 = 298.9 nm (and
pump-laser wavelength of X, = 308 nm): the uppermost transient
(124) Glownia, J. H.; Misewich, J. A.; Sorokin, P. P. J. Chem. Phys. 1990,
92, 3335.
(125) Misewich, J. A.; Glownia, J. H.; Walkup, R. E.; Sorokin, P. P. In
Ultrafast Phenomena VII-, Harris, C. B., Ippen, E. P., Mourou, G. A., Zewail,
A. H., Eds.; Springer Series in Chemical Physics; Springer Verlag: Berlin,
1990; Vol. 53, pp 426-428.
(126) Walkup, R. E.; Misewich, J. A.; Glownia, J. H.; Sorokin, P. P. Phys.
Rev. Lett. 1990, 65, 2366.
Femtosecond Real-Time Probing of Reactions The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7991

Wavelength/nm
Figure 20. Frequency-resolved spectra of atomic Bi at different pump-
Figure 19. Experimental transients and corresponding excited-state po- probe delay times. Spectra of dispersed fluorescence intensity (arbitrary
tential energy curves appropriate to experiments that monitor the time- units) against detection wavelength Xdct arising from excitation of Bi
evolution of Bij dissociation over K,(r). (a) Graphs of LIF signal in- vapor at X, = 308 nm and X2 = 298.9 nm at two pump-probe delay times:
tensity (arbitrary units) versus pump-probe time delay r recorded at (a) < 250 fs; (b) > 1000 fs (adapted from ref 75).
pump and probe wavelengths of ! = 308 nm and X2 = 298.9 nm: the
upper transient depicts off-resonance behavior monitored at *, = 289.8
nm (6p27s JP,/2 — 6p3 2D°3/2); the lower transient shows on-resonance
behavior monitored at *, = 298.9 nm (6p27s 4P3/2 -*· 6p3 2D°3/2). (b)
Schematic diagram of excited-state potential energy curves at energies
£ < 50 X 103 cm"1 above the 4S°3/2 ground atomic level that may be
invoked to explain how both on- and off-resonance FTS data for reaction
22 can be obtained by using a single probe-laser wavelength. Potential
parameters are given in ref 75 (adapted from ref 75).

of Figure 19a, recorded at Xdet = 289.8 nm (6p27s 2P1/2 -*· 6p3

2D°3/2), exhibits off-resonance behavior characterized by a rise
and decay in the observed LIF signal; displayed in the lower
portion are typical on-resonance data monitored at Xdet = 298.9
nm (6p27s 4P3/2 -
6p3 2D°3/2).
The origin of the different time dependences of these two
transients may be explained in terms of a simple model that
involves two high-lying surfaces V2(r) of Bi2 populated by the probe
laser.75 Figure 19b represents a potential energy diagram, similar
in spirit to Figures 1,10, and 14, which may be invoked to interpret
the real-time data displayed in Figure 19a; shown are the disso-
ciative potential Vt(r) and two V2(r) curves correlating with the
6p27s 2P|/2 and 6p27s 4P3/2 + 6p3 4S°3/2 asymptotic atomic levels, Figure 21. [Bi-Bi]4* wave packets. Time-evolution of the wavefunction
respectively. As the wave packet prepared by the pump pulse |iM0> prepared on the dissociative PES V{(r) by optical excitation at
propagates over K,(r) toward 6p3 2D°3/2 + 6p3 4S°3/2 dissociation Xj = 308 nm with a Gaussian-shaped pump-laser pulse of fwhm = 100
products, the probe-laser energy may become resonant with fs centered at t = 0 fs (adapted from ref 75).
transitions to one of the two surfaces V2(r) at two distinct in-
ternuclear configurations: once in the transition-state region 6p3 4S°3/2). As shown in Figure 20b, an additional peak
-*·

corresponding to early-time detection of [Bi—Bi]4* species; and corresponding to the 6p27s 2P1/2 -*· 6p3 2D°3</2 atomic transition
also at larger separations, resulting in long-time detection of final on-resonance with the probe laser at =
X2
= 298.9 nm becomes

Bi(2D°3/2) product.
Figure 20a,b illustrates the early (r < 250 fs) and long-time
( > 1000 fs) dynamics of reaction 22 in the spectral regime and
shows a region of the ultraviolet emission spectrum from Xdct =
280 to 329 nm recorded at two different time delays when Bi vapor
is irradiated by pump- and probe-laser pulses at wavelengths X,
= 308 nm and X2 = 298.9 nm.75 Both spectra exhibit mono-
chromator-resolution-limited peaks corresponding to atomic
fluorescence and broader maxima resulting from scattered laser
light. Figure 20a indicates that, at early times, four transitions
of atomic Bi can be detected at the following wavelengths Xdcl:
290 nm (6p27s 2P1/2 — 6p3 2D°3/2); 294 nm (6p27s 2P3/2 — 6p3
2D°5/2); 303 nm (6p27s 4P5/2
—*
6p3 2D°5/2); 307 nm (6p27s 4P1/2
evident at later times, while the remaining atomic transitions have
diminished in intensity. Thus at pump-probe delay times r <
1000 fs, while Bi2 has not yet completely dissociated, there is no
evidence of the unperturbed Bi atom transition, but several other
emission lines arising from [Bi—Bi]4* transition-state configu-
rations at various stages along the reaction paths leading to final
product states are discernible. For time delays r > 1000 fs, the
separation between constituent atoms of the [Bi—Bi]4* moiety
is sufficiently great such that any interaction between them is
negligible, resulting in essentially free-fragment fluorescence from
atomic Bi.
Figure 21 is analogous to Figure 2 and shows snapshots of the
wave function |^,(<)> propagating over Vx(r) as a function of time
7992 The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 Roberts and Zewail

r/fs
Figure 22. Transient behavior of [Bi—Bi]** calculated by quantum dynamics. Graphs of < 2( )|^2( )> as a function of pump-probe time delay r for
a pump wavelength of X, = 308 nm and various probe wavelengths (X2, nm): (a) 298.9 (6p27s
4P3/2*- 6p3 2D°3/2); (b) 302.5 (6p27s 4P5,2
<-
6p3 2D°5/2);
(c) 298.9 (V2(r) corresponds to the excitation energy of Bi(6pz7s 4P5/2)); (d) 298.9 (V2(r) corresponds to the excitation enegy of Bi(6p27s 2P3/2)). Both
transform-limited laser pulses have Gaussian temporal profiles of fwhm = 100 fs, and values of ( 2( |^2(/)> are normalized with respect to the long-time
asymptote of Figure 22b. Functional forms of the potentials V¡(r), Vy(r), and V2(r) are given in ref 75 (adapted from ref 75).

after optical excitation of Bi2 by a pump-laser pulse at X¡ = 308
nm centered at t = 0. In a manner analogous to that for disso-
ciation of ICN, the wave function initially spreads throughout
the duration of the laser pulse as more population is transferred
to the upper-state potential but thereafter remains highly localized,
with only minimal spreading, for times as long as 2400 fs.75 At
this time, | ( )> samples regions of the reaction coordinate
corresponding to an average Bi—Bi separation of (r) = 26.0 Á,
nearly 10 times longer than the equilibrium bond length of re =
2.66 A.113 For reaction 22a, the wave packet may be considered
to have reached the asymptotic region of the dissociative PES,
where K,(r) is only some 50 cm"1 above the dissociation limit, after
1200 fs. Similar behavior has also been calculated for the wa-
vefunction | ,-( )) initially prepared on the surface Vv(r) leading
to spin-orbit-excited Bi(6p3 2D°5/2) atoms, though in this case the
group velocity of the time-evolving wave packet is much smaller,
with expectation values of (r) = 12.9 Á after 2400 fs and about
15.1 A at t = 3000 fs.75
Graphs of (^2(z)|^2(z)), representing observed LIF signals
average positions of the wave packets | ,( )> and |i/-,.(z)) on the
potentials Vfr) and Vy(r) are (r) = 11.6 and 7.5 A, corresponding
closely to the classically determined values of r1090 = 11.7 A and
r 1500 = 7.5 A obtained from eq 11 with range parameters a,"1 =
a,,"1 = 2.0 A.124
Figure 22c,d displays off-resonance transients for the two exit
channels leading to the 2D°7 term. These data were computed
for a probe-laser wavelength of X2 = 298.9 nm detuned by 3625
and 577 cm"1, respectively, from the appropriate resonance
transitions for free atomic absorption (X2 = 269.7 (6p27s 4P5/2
*-
6p3 2D°3/2) and 293.8 nm (6p27s 2P3/2
*-
6p3 2D°s/2)), and
correspond to early-time detection of [Bi—Bi]** wave packets at
transition-state regions of configuration space.75 Both transients
show a rise and decay in signal intensity as the wave packets on
Vfr) and Vv{r) pass through the optically coupled region defined
by the spectrum of the probe-laser pulse, with maxima located
at delay times r of approximately 220 and 670 fs. At these delay
times, the average positions sampled by |i^i(z)> and |^v(t)) are
(r) 0.34 and 3.9 A along the dissociative potentials Vfr) and
~

calculated by the quantum-dynamical model of section II.B as
before, are displayed in Figure 22 for reaction according to both
equations 22a and 22b. Pump- and probe-laser frequencies were
chosen to match those employed experimentally.75 Figure 22a,b
depicts on-resonance behavior corresponding to detection of Bi
atoms in their 6p3 2D°3/2 and 6p3 2D°5/2 spin-orbit levels at long
times following dissociation via exit channels 22a and 22b. These
plots are characterized by dissociation times 1/2 of = 990 and
1480 fs, respectively, in reasonable quantitative agreement with
the corresponding experimental estimates of 1/2 = 1090 ± 50
and 1500 ± 50 fs.75 At delay times r = 1090 and 1500 fs, the
Vy(r). A comparison of these results with the appropriate FTS
data and their interpretation in terms of the topological charac-
teristics of the reactive PESs has been given previously;75 here
we simply note that such data are in broad qualitative, though
not quantitative, agreement with experimental results. The dif-
ference between calculated transients and those recorded by FTS
experiments has been attributed75 to a lack of sophistication in
the selection of model potentials K,(r) and Vy(r), which were
originally chosen by Sorokin and co-workers124 to obey the simple
exponential dependence on interfragment distance given by eq 16
such that the long-time (asymptotic) behavior predicted from
Femtosecond Real-Time Probing of Reactions
trajectory calculations was in approximate quantitative accord
with experiment.
The overall shapes of the on- and off-resonance transients for
reaction 22 obtained both experimentally and theoretically are
qualitatively similar in form to analogous data for the dissociation
of ICN given in section III: this fact in itself suggests that
fragmentation of Bi2 via the two exit channels giving rise to the
ground-state term and 2D°3z2 and 2D°5/2 products proceeds over
PESs that are predominantly repulsive in character at distances
beyond the Franck-Condon region. It may be noted that values
of the dissociation times t1/2 for reactions 22a and 22b are ap-
proximately 5-7 times longer than those computed and determined
experimentally for ICN dissociation and that the off-resonance
transients are correspondingly broader in the former case. These
effects may readily be anticipated on simple kinematic and dy-
namical grounds (assuming little internal excitation of the I and
CN products of reaction 1); the reduced mass of Bi2 is µ = 104.490
a.u compared to µ = 21.591 a.u. for ICN while the translational
energies available to dissociation products are £av 6550 and 1053
cm"1 for reactions la and lb (initiated by photolysis radiation at
Xt
= 306 nm) and Eav = 5102 and 1083 cm'1 for reactions 22a
and 22b (with ! = 308 nm), coupled with the assumed functional
forms of the reactive potentials in both cases.75,123
V. Summary and Conclusions
The femtosecond dynamics of systems involving repul-
sive,1"6,75,94,103,104 bound,94"97,118 and quasibound98"102 PESs have
now been studied in a number of specific cases. Each of these
potentials give rise to dynamical effects that are characterized
in real time by the following phenomena: localization of the initial
wave packet on the reactive PES prepared by the pump-laser pulse;
subsequent spreading and decreasing amplitude of the wave packet
as a function of time; and, for bound and quasi-bound PESs,
oscillatory motion. In the bound and quasibound systems studied
thus far94"102,118 the wave function is highly localized (of angstrom
or subangstrom width) and spreading of the time-evolving wave
packet is quite slow; dephasing and quantum rephasing can be
observed on the picosecond time scale, while the nuclear dynamics
occurs over periods of femtoseconds.
For dissociative processes that take place over purely repulsive
PESs such as the fragmentation of ICN reported in this paper,
and also the dissociation of Bi2,75 the initial wave packet samples
a larger region of configuration space; not because of spreading
effects inherent in the time-evolution of the wave function,115 but
merely because of the finite pulse width of the pump-laser pulse
and the very nature of the dissociative potential controlling re-
action. From an experimental perspective, this entails the de-
convolution of the temporal response function of the pump- and
probe-laser pulses in order to determine the time constants of the
nuclear separation dynamics, as explained elsewhere4,5 Theo-
retically, the preparation and probing effects of the laser pulses
are explicitly taken into account in solving the Schrodinger
equation (section II.B) or the classical equations of motion (section
II.C) for the reaction dynamics.
In this article, quantum- and classical-mechanical calculations
of the time-dependent dynamics of the dissociation of ICN have
been presented and compared with experimental measurements
obtained by the FTS technique; a previous study75 of the atom-
ization of Bi2 has also been summarized and appropriate com-
parisons made. We consider that our calculated FTS transients
are in reasonable qualitative agreement with both experimental
data2"5 and previous theoretical work.4,5,42,44,51,58"63 The ability
of classical mechanics to describe the reaction dynamics of such
The Journal of Physical Chemistry, Vol. 95, No. 21, 1991 7993
processes over ultrashort time scales has been tested and evaluated;
apart from failing to account for the purely quantum effects of
rephasing and spreading of the dissociating wave packet, a re-
markable degree of correspondence between quantum dynamics
and the “single-trajectory” classical model62 in describing nuclear
motion over these time scales is exhibited. It should be mentioned
that the effect of wave packet spreading could be taken into
account by carrying out a multitrajectory classical treatment with
a distribution of initial velocities and positions of the dissociating
system.
By variation of the parameters describing the simple exponential
form of the dissociative potential function V, (r) invoked throughout
this study, we have further investigated the effect on the expected
FTS transients of changing the nature of the force field experi-
enced by the initial wave packet prepared on the reactive potential.
In this way, the acceleration of the wave packet as it propagates
away from the Franck-Condon region of the reactive potential
is altered, and its effect on the bond-breaking time and lifetimes
of transition-state configurations examined. Similarly, inclusion
of a repulsive component in the form of the high-lying potential
curve V2(r) populated by the probe-laser pulse, in addition to that
of Vfr), has made it possible to investigate how changes in the
dimensions and position of the detection window projected onto
the reactive potential Vx{r) are manifested in terms of the
time-resolved “snapshots” of the reaction. By fixing the probe
wavelength and changing the total energy available to dissociation
products, the dynamics on V¡(r) may be isolated and mapped out;63
by keeping the available energy constant and varying the probe
wavelength, the separation AV2¡ = |V2(r) Vfr)\ between po-
-
tential energy curves can be determined, as discussed in section
III.D. Such an approach has been applied experimentally to isolate
the dynamics of reaction 1 by variation of the pump-laser
wavelength X,,5 while the shapes of both PESs V2(r) and Vfr)
governing the observed dynamics of the predissociation of Nal
have been examined in detail by independent variation of both
pump- and probe-laser energies.99,100,102 As confirmed by ex-
periment,2'5 the results of section III.D demonstrate the sensitive
nature of FTS measurements to changes in the characteristics of
the two potentials Vfr) and V2(r).
The addition of a centrifugal barrier to the PES controlling
dissociation has been briefly considered and preliminary results
communicated. Finally, the effect of changing the kinematics of
direct dissociation was investigated by analysis of the fragmen-
tation of the behavior Bi2 molecule. The predictive power of
classical mechanics for both ICN and Bi2 systems is remarkable
and consistent with quantum dynamical calculations.
Acknowledgment. We are grateful to the National Science
Foundation and Air Force Office of Scientific Research for fi-
nancial support. G.R. thanks SERC for the award of a NATO
Postdoctoral Fellowship, during the tenure of which this work was
carried out. We also thank the referees for a thorough review
of this manuscript and for useful suggestions.
Note Added in Proof. In addition to considering the effect of
centrifugal energy in the dissociation of ICN, we have also carried
out an analogous investigation involving the inclusion of an at-
tractive term to the reactive potential due to the dipole/induced
dipole interaction between CN and I fragments. Addition of this
attractive term to the potential modifies eq 19 to give V,efr(r) =
Vfr) + [/(/ + 1)^2/2µ 2] C6/r* where C6 = Mcn2“i/(4™o)2
-
= 53 315 cm'1 Á6 (µ0 is the dipole moment of CN and «| is the
polarizability of i). The results of this study will be detailed
elsewhere123 once our calculations have been completed.