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The Photophysics of a Polar Molecule in a Nonpolar Cryogenic Glass - The

Effects of Dimerization on (1-Butyl-4-(1H-inden-1-ylidene)-1,4-
dihydropyridine (BIDP)

Article  in  The Journal of Physical Chemistry A · October 2010

DOI: 10.1021/jp1047375 · Source: PubMed

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 J. Phys. Chem. A 2010, 114, 10563–10574 10563

The Photophysics of a Polar Molecule in a Nonpolar Cryogenic Glass - The Effects of

Dimerization on (1-Butyl-4-(1H-inden-1-ylidene)-1,4-dihydropyridine (BIDP)

Anat Kahan, Boris Bazanov, and Yehuda Haas*

Institute of Chemistry and the Farkas Center for Light Induced Processes, the Hebrew UniVersity of Jerusalem,
Jerusalem, Israel
ReceiVed: May 24, 2010; ReVised Manuscript ReceiVed: August 9, 2010

The first excited state of BIDP was shown in a previous communication to exhibit an ultrafast decay in fluid
nonpolar, nonprotic solutions due to the presence of a S1/S0 conical intersection (CI). In frozen polar and
nonpolar glasses a strong fluorescence was observed, rationalized by the hindering of the internal torsion
required to reach the geometry of the CI. Complete analysis of the data was hampered by some unusual
observations in nonpolar glasses. In this paper we show that they can be explained by assuming dimer formation,
with a formation constant of Keq ) (4 ( 3) × 105 M-1 at 83 K and ∆Hdim ) 7 ( 2 kcal/mol. A complete
analysis of the spectra is presented, and fluorescence quantum yields of the monomer and dimer are reported.
Efficient self-quenching is found, with a Stern Volmer constant, KSV ) (1.5 ( 0.1) × 106 M-1, assigned to
static quenching. The dimer absorption spectrum was extracted from the data and is compared to Kasha’s
exciton model and to quantum chemical (QC) calculations. The basic features of exciton splitting are reproduced
by quantum mechanical calculations, but complete quantitative agreement of the QC computations with the
experimental results is not attained. The previous analysis of the monomer spectra using the displaced harmonic
oscillator model is extended to the more demanding conditions prevailing at cryogenic temperatures. The
derived ∆Hdim is in good agreement with other dimers formation enthalpies and with the quantum mechanical
calculation presented. The new analysis corrects τf in MCHIP to 2.9 × 10-13 s, somewhat smaller than the
value reported in polar solvent in a previous communication, thereby strengthening the assumption that polarity
can reduce the efficiency of CI.

I. Introduction SCHEME 1: Structure of BIDP

The photophysics of 1-butyl-4-(1H-inden-1-ylidene)-1,4-
dihydropyridine (BIDP, Scheme 1) were recently discussed
experimentally1,2 and theoretically.3 The molecule is a model
molecule that was used to explore solvent and electric field
effects on conical intersection (CI).1,4 This molecule belongs
to a family of molecules such as merocyanines5 and 1-fluoro-
2,4-hexadiene,6 whose CIs were considered to be controlled by
the solvent. In fluid solution’s internal conversion was found
to be very efficient in all solvents as confirmed by the absence
of fluorescence, whereas in glassy solutions at cryogenic
ization in cryogenic temperatures is a well-known phenomenon,
temperatures, the fluorescence yield was found to be high (0.59
reported12 already over 50 years ago. In addition to new spectral
in a polar solvent). In nonpolar solvents quantitative measure-
features, dimer formation often also decreases the emission
ments were hampered by dramatic changes of the fluorescence
intensity of the monomer (self-quenching). The classical
spectra. It was suggested that in the nonpolar glasses aggregation
Stern-Volmer mechanism (eq 1) is frequently a satisfactory
takes place, leading to more complicated photophysical behavior.
approximation.
In this paper we report novel measurements performed to check
this hypothesis.
BIDP, as other polar molecules having an extended conju- φf(0)
gated π-electron system, has a well-known tendency to form ) 1 + KSV[Q] (1)
φf(Q)
dimers and higher aggregates, especially in nonpolar solvents.
The phenomenon has been extensively studied due to its
theoretical and practical importance.7-10 A well-known, physi- In fluid environments, dynamic quenching dominates and the
cally transparent model has been developed by Kasha and co- Stern-Volmer constant KSV is interpreted as KSV ) (kq)/(kf),
workers.11 This exciton model predicts the formation of dimers where kq is the bimolecular quenching rate constant, often
and higher aggregates, and analyzes the resulting absorption equaling the diffusion coefficient, and kf is the inverse lifetime
and emission spectra of the aggregates in terms of the spectra of the fluorescent molecule in the absence of the quencher (in
of the monomer constituents and the dimer structure. Dimer- the case of self-quenching, extrapolated to zero concentration).
In glasses where translational motion is restricted, static
* To whom correspondence should be addressed. Fax: +97225618033. quenching is more likely.13 When static quenching results from
10.1021/jp1047375  2010 American Chemical Society
Published on Web 09/10/2010
10564 J. Phys. Chem. A, Vol. 114, No. 39, 2010
the formation of a complex (or dimer) in the ground state KSV
often equals the dimerization equilibrium constant Keq for the
reaction pair
k1
2M 98 D
k-1 (2)
D 98 2M
the equilibrium constant, Keq, is given by
k1 [D]eq
Keq ) ) (3)
k-1 [M]2eq
Using the exciton model as a guide, it is shown that the dimer
spectrum can be extracted from the low temperature absorption
and emission spectra. The data are also compared to DFT
calculations of the ground state dimer structure, and TDDFT
calculations of the dimer spectrum.
Experimental and Computational Details
Experimental Details. BIDP was prepared and purified using
literature procedures.14,15 It was characterized by visible and
NMR spectra and by its fluorescence. The solvents used were
methylcyclohexane (MCH, Sigma-Aldrich, spectroscopic grade),
2-methyl-butane (isopentane, IP, Sigma-Aldrich, HPLC grade),
and 2-methyltetrahydrofurane (2MTHF, Sigma-Aldrich, >99%).
Low temperature spectra were taken in a methylcyclohexane/
isopentane (MCHIP, 2:3) composition. This solvent was thor-
oughly dried in preliminary experiments (sodium metal) to
ensure the exclusion of hydrogen bonding, water aggregates,
etc. In further experiments it was found that the solvent was
water-free, and it was used as is.
For spectroscopic experiments at cryogenic temperatures, a
homemade apparatus was used, built around an Oxford Instru-
ments double-wall cryostat equipped with a liquid nitrogen
container and heating circuit operated by a temperature controller
(Eurotherm Inc., model 2216 L). The white light source (Ocean
Optics Inc., halogen-deuterium, UV-vis-NIR DT-MINI-2-GS)
and miniature spectrometer (Ocean Optics Inc., USB-4000)
collinearly coupled through the cryogenic system by quartz
fibers were used in absorption experiments. For fluorescence
and excitation profiles a white light source (Hamamatsu CM
150 W xenon-Arc-Lamp E7536) at perpendicular configuration
was used. For the fluorescence experiments the excitation
wavelength was selected by passing the light beam through a
monochromator, equipped with a 2400 L/mm grating. To
calculate quantum yield (QY), coumarine 540 in acetonitrile
was used as a reference (QY ) 0.63).16 For excitation profiles
measurements the monochromator was used in order to change
the excitation wavelength and a R928 photomultiplier, with
interference filters at 560 or 660 nm (40 nm fwhm), were used
to collect the emitted light. Prior to the measurements the
solution was saturated with dry nitrogen gas to avoid photo-
oxidation during spectroscopic experiments.2 All measurements
were carried out in a cylindrical quartz cuvette, 13 mm inner
diameter.
Computational Details. Quantum mechanical (QM) calcula-
tions were used to analyze different dimer geometries and their
effect on the spectroscopic characterizations. Calculations were
performed using the PCGAMESS programs suite17 and the
Kahan et al.
QCHEM program suite.18 The calculations were made for the
IDP molecule, without the n-butyl tail connected to the pyridine
ring, which is a change that does not effect the electronic
distribution. The monomer ground state structure was fully
optimized using B3LYP/6-31G(d) calculation, and the optimized
structure was used for all other calculations. TDDFT/B3LYP/
6-31G(d) calculations were used for excited states of the
monomer. In addition, TDDFT/BNL/6-31G(d) calculations were
preformed. This functional, developed by Baer and Livshits,19
helps to correct long-range behavior by a splitting functional
and a complementary exchange-correlation functional, both
depend on tuning factor γ. The tuning process20 gave γ ) 222.
This functional was chosen as it appears to be more suitable
for charge transfer (CT) states, especially for systems too large
for CAS calculations, such as BIDP dimers, and should yield
better agreement with experiment than the B3LYP functional.21
For comparison, ground state was also calculated using the MP2
energy correction, to check whether DFT can be used to
compute intermolecular interactions.22 Different dimer structures
were calculated using the three methods, based on the optimized
structure of the monomer. Two of the structures are based on
Kasha’s “in line” and “parallel” dimer geometries, with the two
dipole moments in line, pointing in the same direction (dimer1,
see Table 1 in the Results section) or parallel, having opposite
directions (dimer2). Dimer3 was inspired by the T structure of
the benzene dimer. Most of the structures were previously
calculated for pyridine dimers.23 For dimer1, 2, and 3, different
distances between the monomers were calculated, and in the
range between 3 and 5 Å only minor differences were found.
As a result, a 4 Å distance was chosen. Other structures were
tested starting with various geometries and performing full
optimization; the most stable in energy is labeled dimer4. It
has an anti parallel structure, with a 3.78 Å distance between
the monomers, with the center of mass of one monomer shifted
from the other by 5.16 Å (See Table 1).
The 6-31G(d) basis set was the largest basis for which the
optimization process converged, and was consequently chosen
for all further calculations. For a comparison, single-point
calculations using the 6-311G(2d) basis set were also used
in TDDFT/B3LYP calculations. Other geometries were
calculated but were found to be less stable than those four,
which were therefore used in order to discuss the experi-
mental results.
The PCM model24,25 was used to simulate the solvent effect
of cyclohexane on dimer4 using DFT/B3LYP/6-31G(d). A few
trimer structures (Scheme S1 in the Supporting Information)
were also calculated, using B3LYP functional, but as their
contribution to the absorption spectra was found to be marginal,
without any new contribution that can explain the absorption
spectrum, no TDDFT/BNL calculations were performed on
them.
As in ref 1, an analysis separating the observed experimental
spectrum to the first two allowed transitions theory predicts for
the monomer, S0-S1 and S0-S31 was performed. The displaced
harmonic oscillator (DHO) model, developed by Heller, Myers,
and Mathies,26,27 was used, (eq 4).
[ ]
4π2e2M2EL -(E0 - Ej 0)2
σA(EL) ) exp ×
3pcn 2θ
[∫
∞
exp[i(EL - V)t/p]exp(-Γt/p) × (4)
-∞
]
∏ [exp{-sk[1 - exp(-iωkt)]}]dt
k)1
Photophysics of a Polar Molecule in a Nonpolar Glass
Figure 1. (a) The UV-vis absorption spectrum of BIDP in MCHIP as a function of the temperature ([M]corr 83K
spectra at three temperaturess298, 198, and 143 Ksshowing more clearly three main temperature-dependent features of BIDP absorption. (b) The
OD at 395 nm (black), 450 nm (red), and 505 nm (green) as a function of the temperature. Three regions appear to characterize the temperature
dependence of the absorption; the transition temperatures are T1 ) 147 K and T2 ) 200 K. See text for more details.
σA(EL) is the absorption cross section, EL is the energy of the
incident photon, e is the charge of the electron, M is the
electronic transition length between the ground and excited
electronic states, p is Planck’s constant, c is the velocity of light,
and n is the refraction index. θ is the inhomogeneous width,
and each band is broadened inhomogeneous. E0 is the energy
separation between the lowest vibrational level of the ground
state and the electronic excited state, exp(-Γt/p) is a damping
factor with Γ as the homogeneous line-width, ωk is the frequency
of the k mode, sk ) ∆k2/2, and ∆k is a displacement between
ground and excited state harmonic surfaces. The model was used
to fit the excitation spectrum at 83 K of monomer absorption
(Figure S1) and the absorption spectrum at 298 K (detailed
information in Table S1). Several iterations were performed until
the only major changes between room temperature and low
temperature were the homogeneous and the inhomogeneous line
width factors, and the refractive index, n, while the other
parameters should not change much with temperature. The
separation made it possible to calculate the oscillator strength
for each transition, and the radiative rate constant kf0 was
calculated using the Strickler-Berg equation28 (5).
∫ I(ν̃)dν̃ ε(ν̃)
kf0 )
1
) 2.88 × 10-9n2 ∫ dν̃ ≈
τ0 ∫ I(ν̃)ν̃-3dν̃ ν̃
0.667n2〈ν̃〉2avf (5)
τ0 is the radiative lifetime, n is the refractive index of the solvent,
I is the fluorescence emission, ν˜ is wavenumber, and ε(ν˜) is
the extinction coefficient, f is oscillator strength of the transition,
〈ν〉av is the average wavenumber corresponding to the 0-0
transition.
Attempts to simulate dimer absorption using the DHO model
were also made. The QM calculated transitions were used, and
were shifted all by the same amount. The shift is a result of the
difference between the experiment and the QM calculations,
and also a result of the difference between the Franck-Condon
QM calculation results and the zero-zero energy in the DHO
J. Phys. Chem. A, Vol. 114, No. 39, 2010 10565
) 3.3 × 10-5). Inset: normalized
model. The amount of shifting was determined by the shift
needed for comparison to the monomer excitation spectrum at
83 K at low concentration.
Experimental and Computational Results
Experimental Results. As briefly discussed in ref 1 and
shown in more detail in Figure 1, the absorption spectrum of
BIDP in MCHIP depends strongly on temperature. Whereas at
room temperature the spectrum is similar to that in more polar
solvents (2-methyltetrahydrofuran (MTHF), acetonitrile), in the
glassy solvent at 83 K the spectrum is much broader (Figures
3 and 5 in ref 1). A second important observation is that at 83
K the molecule fluoresces, and its emission spectrum bears an
approximate mirror image to the absorption spectrum in polar
solvents, whereas in MCHIP glass no such relation is observed.
A third noteworthy difference was that in MTHF the fluores-
cence quantum yield (0.57) was much higher than in MCHIP
glass (∼0.1). It was suggested that, although the BIDP
concentration was relatively low (5 × 10-5 M) dimerization
might be involved in the low temperature samples. Indeed,
preliminary experiments showed that the shape of the absorption
spectrum changed upon reducing the solute’s concentration.
It transpired that the concentration range in which further
dilution did not change the spectrum’s shape was around 3 ×
10-7 M. Unfortunately absorption spectra in this range are too
noisy for quantitative analysis, so that fluorescence excitation
spectra were used to obtain the absorption line-shape at these
low concentrations. In this concentration range (∼10-7 M) the
emission spectrum was found, in contrast with higher concentra-
tions, to be independent of the excitation wavelength. These
data indicate that a single species is present in the dilute
solutions, whereas at least two are present at higher concentrations.
Figure 2a shows the absorption/excitation spectra recorded
for BIDP in MCHIP glass at two different concentrations, 3.6
× 10-7 M and 5.4 × 10-5 M. The main differences are the
much broader spectrum at the higher concentration and the more
prominent vibronic structure in the lower concentration. These
features bring to mind the predictions of the exciton model of
Kasha for parallel transitions: two electronically excited dimer
levels are expected, an allowed one shifted to the blue with
10566 J. Phys. Chem. A, Vol. 114, No. 39, 2010
TABLE 1: The Energy of IDP Monomer and Dimer and the Difference in Energy between Two Monomers and Dimer,
Calculated by TDDFT/B3LYP/6-31G(d), by TDDFT/BNL/6-31G(d) and by MP2/6-31G(d), as well as Two Trimer Structures
Calculated by TDDFT/B3LYP/6-31G(d)
respect to the monomer, and a forbidden one shifted to the red.
Several experiments were run at different initial concentrations,
and the dimer spectrum was extracted by subtracting the
monomer spectrum from the total one.
In order to do so, we assume that at low concentration of
BIDP (∼10-7 M) the excitation spectrum is due to the spectrum
of monomer only. Furthermore, the oscillator strength of the
monomer at 83 K was assumed to differ only slightly from that
at room temperature. Thus, by taking into account also the
changes in the refraction index and in the density of the solvent,
it is possible to estimate the extinction coefficients at 83 K. A
further assumption is that at 470 nm the absorption is due to
the monomer only, whereas for the red and blue sides of it we
used the equation ODtot ) εM[M]l + ODD. That way we could
obtain the monomer and dimer concentrations, and their relative
contributions. This procedure was repeated for several initial
total concentrations of BIDP.
Figure 2b displays the spectrum, assigned to the dimer,
resulting from the subtraction of the monomer contribution from
the complete experimental spectrum. The dimer absorption
exhibits two main bands, a broad strong one, about 5000 cm-1
fwhm, blue-shifted with respect to the monomer, and a weaker
one, narrower, about 1100 cm-1 fwhm, that is red-shifted. The
splitting between their maxima is about 6000 cm-1, with 4000
cm-1 (2000 cm-1) from the monomer maximum absorption to
the blue (red).
The monomer emission spectrum was measured directly using
a dilute solution, and the dimer spectrum was obtained using a
Kahan et al.
procedure similar to that applied to the absorption spectrum.
The subtraction was made under the approximation that the
emission at 525 nm and shorter wavelengths is due to the
monomer species only.
The emission spectra are displayed, along with the absorption
spectra, in Figure 3. It is seen that an approximate mirror image
relation is found for the monomer, and also an approximate
one between the dimer emission and the weak, red-shifted,
absorption band centered at 505 nm (for comparison, see
Figure 5 in ref 1).
The separation of the spectra allowed the measurement of
the fluorescence quantum yields of the monomer and dimer.
The case of the monomer is straightforward, provided the molar
absorption coefficient in the MCHIP glass is known. An
approximate value can be obtained from the absorption spectra,
but as mentioned above they were too noisy to be reliable. Under
the assumption that the oscillator strength of the transitions is
independent of the temperature, the molar absorption coefficient
values at room temperature were used to deduce the low
temperature ones. Using this procedure, and the solvent’s density
temperature dependence, the molar absorption coefficient of the
monomer at the maximum (457 nm) is 30000 ( 3000 M-1 cm-1
(room temperature value is
(λmax) ) 21 6001), and the molar
absorption coefficient of the dimer obtained upon separation of
the spectra is 21 000 ( 2000 M-1 cm-1 at λmax ) 390 nm. These
values lead to successful reconstruction of the low temperature
spectra (Figure S4). The low temperature values are consistent
with the narrowing of the monomer band upon cooling.
Photophysics of a Polar Molecule in a Nonpolar Glass J. Phys. Chem. A, Vol. 114, No. 39, 2010 10567

Figure 2. The proposed partition of the BIDP absorption spectrum to the contributions of the monomer and the dimer in MCHIP at 83 K. (a) Full
line: The total absorption spectrum, 5.4 × 10-5 M; Dashed line: The monomer excitation spectrum detected at 660 nm, 3.6 × 10-7 M. (b) The
dimer spectra extracted from spectra shown in (a). See text for details.

Figure 3. Absorption/excitation and emission spectra of BIDP monomer (a) and dimer (b), normalized, at 83 K in MCHIP. (a) Full line: excitation
spectrum, λem ) 560 nm, dashed: emission spectrum, λexc ) 450 nm. (b) Derived absorption (full line) and emission spectra (dashed) of BIDP
dimer.

With the monomer absorption coefficient at hand, the reported in ref 1, in which the dimer contribution was not
fluorescence quantum yield at low concentration at 83 K was considered. It was also observed that the monomer quantum
found to be 0.9 ( 0.1. This value is much higher than that yield strongly decreased as the BIDP concentration was
10568 J. Phys. Chem. A, Vol. 114, No. 39, 2010 Kahan et al.

TABLE 2: Fluorescence Quantum Yields of the Monomer The temperature dependence of the absorption of BIDP in
As a Function of the Nominal BIDP Concentrationa MCHIP was shown in Figure 1. Three main temperature regions
tot
OD457 nm (RT)
83K
[M]corr φ(Q) (φ(0))/(φ(Q)) can be distinguished in the spectrum. The first one is between
-6 80 and 180 K, where the broad spectra display three maxima,
0.16 7.4 × 10 0.08 + 0.01 12.5
0.13 5.9 × 10-6 0.11 + 0.01 9.1 at 505, 450, and 395 nm, which were assigned to a combination
0.10 4.4 × 10-6 0.15 + 0.01 6.7 of the monomer and the dimer, as mentioned above. In the
0.08 3.7 × 10-6 0.16 + 0.02 6.3 second temperature range, (180-220 K), the spectrum is still
0.06 3.0 × 10-6 0.17 + 0.02 5.9 quite broad, but the peaks at 505 nm and especially at 395 nm
0.05 2.2 × 10-6 0.24 + 0.02 4.2 are less prominent. The third region is from 220 to 298 K, a
0.03 1.5 × 10-6 0.40 + 0.04 2.5 region where the monomer spectrum is dominant and no dimer
0.02 7.4 × 10-7 0.91 + 0.09 1.1
contribution can be discerned. A large decrease of the absorption
a 83K
[M]corr is the corrected concentration at 83 K for volume intensity is noted as the system is cooled.
decrease; φ (Q) is the quantum efficiency of BIDP monomer Next, Van’t-Hoff’s equation was used to derive the dimer-
83K
fluorescence when the concentration equals [M]corr (self quenching).
ization enthalpy ∆Hdim: (d(ln Keq))/(d(1/T))) ) -(∆Hdim/R). At
each temperature, Keq can be expressed by Keq )[D]/[M]2
)(([M]0 - [M]) × 0.5)/[M]2. Using the beer-Lambert law, [M]
can be expressed by(ODM)/(εM,ν × l), where l is the cell length,
εM,ν is the extinction coefficient and is temperature dependent,
and ODM is the absorbance of the monomer, which is also
temperature dependent. [M]0 has to be corrected for the volume
change incurred upon temperature change. The absorbance of
BIDP in MCHIP is due to both dimer and monomer at low
temperatures; in order to separate them we used the facts that
the excitation spectrum of BIDP in MCHIP at low concentra-
tions is very similar to BIDP in 2MTHF and that in 2MTHF
no dimer is observed even at 83 K, at all concentrations (Figure
S2). Therefore, we calculated the monomer spectra at different
temperatures for BIDP in 2MTHF, by performing a DHO fit
and using the resulting homogeneous and inhomogeneous width
parameters at each temperature for BIDP in MCHIP, to get εM,ν
as a function of temperature. By scaling it to the experimental
spectra we got ODM as a function of temperature (Figure 5). It
Figure 4. Stern-Volmer plot for the self-quenching of BIDP at 83 was also possible to subtract these monomer spectra from the
K. Squares: (φf(0))/(φf([M])), the ratio of the quantum yield at the lowest experimental absorbance bands to get the dimer line shapes (See
BIDP concentration used, to the QY at higher monomer concentrations, Figure 5b). The procedures used to find Keq at each temperature
vs nominal concentration. Straight line: a linear fit that gives KSV )
(1.5 ( 0.1) × 106 M-1. and the results of detailed calculations are listed in Table S3
(Supporting Information), and a plot of ln Keq versus 1/T is
shown in Figure 6. A straight line from 298 to 198 K yields
increased. In order to obtain quantitative data, the concentrations ∆Hdim ) 7 ( 2 kcal/mol. In the range from 198 to 83 K, Keq
of the dimer and monomer were determined in the total appears to be essentially constant.
concentration range (corrected for 83 K) 7.4 × 10-6 to 5.0 × Computational Results. The main results of the quantum
10-5 M using the separated spectra. From these data, an average chemical calculations are summarized in Table 1. In all cases,
value of Keq ) (4 ( 3) × 105 M-1 was derived using eq 3 (at the calculated dimer structures are more stable than two
83 K). In spite of the relatively large error, the basic assumption separated monomers by 0.3-14 kcal/mol. dimer1, dimer2, and
that dimer formation is the main cause for the spectral changes dimer3 are stable structures and have unique symmetry and/or
appears to be supported by the fact that the equilibrium constant distance constructions. Dimer1 is an in-line structure with Cs
calculated at 83 K for these various concentrations has a realistic symmetry and 4 Å distance between the nearest atoms. Both
value. dipoles of the monomers are aligned along the same direction,
Table S2 of the Supporting Information summarizes the leading to a slight stability, of 0.27 (0.36) kcal/mol using the
results for different nominal concentrations of BIDP. Due to B3LYP (BNL) functionals compared to the two separated
S/N ratio considerations, the monomer and dimer concentrations monomers. Dimer2, which is more stable than dimer1 by 1.6
could be reliably extracted by the subtraction method only for (7.7) kcal/mol at 4A distance, has antiparallel structure, which
solutions whose room temperature OD exceeded 0.2 (total probably increases the dipole interaction that stabilizes it. The
concentration > 4 × 10-6 M). The small variability of the corresponding parallel structure (not shown) is less stable than
equilibrium constant supports the hypothesis that dimerization two separate monomers at all distances checked, from 3 to 7
is the major aggregation process in the concentration range used Å. Dimer3 is a T structure with the two dipoles in antiparallel
in this work, and that formation of bigger adducts for the configuration, which is stabilized by 1.5 (2.5) kcal/mol. Dimer4
detected wavelengths may be neglected in the concentra- was the most stable structure found from several optimization
tion range used. Table 2 displays the results of separation of processes employing DFT/B3LYP starting at different dimer
the fluorescence to monomer and dimer contributions, using the geometries. Dimer4 is stable by 8 kcal/mol (14 kcal/mol) at
derived Keq. The quenching process was analyzed using the the B3LYP (BNL) level, and in solution (B3LYP/PCM) dimer4
Stern-Volmer equation (eq 1). Figure 4 shows that a linear is more stable by 5 kcal/mol. The MP2 calculations for the
relationship is obtained for the self-quenching process with KSV ground state strengthen those results and show the same range
) (1.5 ( 0.1) × 106 M-1. of stabilization energies for all dimers. For another comparison
Photophysics of a Polar Molecule in a Nonpolar Glass
Figure 5. (a) The dimer spectra as extrapolated from the difference between the total absorbance and the monomer DHO fit, at different temperatures
83K
([M]corr ) 3.3 × 10-5). (b) An example for deriving the dimer spectra in (a). Black: experimental BIDP absorbance at 163 K (other temperatures
at figure 1). Red: the monomer line shape based on the DHO model analysis (see text). Blue: the dimer spectrum as obtained from the difference
from the total absorbance and the monomer DHO fit, at 163 K.
Figure 6. A van’t Hoff plot for BIDP in MCHIP. The region from 298
to 198 K yields ∆Hdim ) 7 ( 2 kcal/mol. See Table S3 for details.
6-311G(2d) basis set was also used in TDDFT/B3LYP calcula-
tions, and the stability energies are 10% larger at the most (Table
S4). Since the differences are small for the large basis sets used,
the basis set superposition error (BSSE) correction is not
considered important (See ref 29).
Two trimer structures (based on dimer1 and dimer2, respec-
tively) are presented in Table 1, using the B3LYP functional,
were found to show no extra stability.
Two allowed transitions of the monomer that have oscillator
strength larger than 0.1 were found by both TDDFT functionals,
B3LYP and BNL, as in previous CASSCF calculations (ref 1).
The B3LYP functional predict that transitions S0-S1 and S0-S3
are allowed (in agreement with the CAS calculations), with
oscillator strengths of 0.21 and 0.49 respectively. Using BNL
functional the allowed transitions are S0-S1 and S0-S2 with
oscillator strengths of 0.50 and 0.18 respectively. A splitting
J. Phys. Chem. A, Vol. 114, No. 39, 2010 10569
of the monomer transitions was obtained in all dimers structures.
An allowed monomer electronic transitions was split to an
allowed and a forbidden transition, in line with Kasha’s model11
for dimer spectra.
The character of the transitions can be analyzed considering
the main orbitals involved in the transition. The orbitals of two
monomers coming close to each other interact to create dimer
orbitals. There are two types of dimers orbitals, (i) those formed
by combination or anticombination of monomer orbitals and
(ii) those in which the electronic distribution resides on one of
the monomers only (This can be viewed as a monomer orbital
“solvated” by the other monomer). Dimer4 was chosen for a
qualitative analysis as it is the most stable dimer and also has
both types of dimer orbitals, (i) and (ii), and as a result it also
has CT transitions. Scheme 2 shows the orbitals involved in
the main optical transitions of the monomer and in dimer4, at
the TDDFT/B3LYP/6-31G(d) level. On the left panel the
dominant orbitals of the monomer in the S0-S1 and S0-S3
transitions are shown. Both involve transitions from orbital 50
to 52 and from 51 to 52, but with different weights. Both have
a mixed character, partly ππ* and partly intramolecular CT.
The shapes of the orbitals of dimer4 are displayed in the middle
panel. Orbitals 99 and 100 are dimer orbitals that are mainly
type (ii), originating from orbitals 50 of the two monomers,
while retaining the electronic distribution of the monomers.
Orbitals 101 and 102 are mainly type (ii), originating from
orbitals 51 of the two monomers and orbitals 103-104 are
combination and anticombination of orbitals 52 in the monomers
(type (i)). The dimer transitions S0-S1 (a), S0-S1 (b), S0-S3
(a), and S0-S3 (b) transitions have an intermolecular CT
character, where the electronic density distribution is mostly
on one molecule of the dimer in the ground state and is
transferred to an orbital in which the electronic distribution is
spread over the whole dimer. The type (ii) transitions split to
allowed and less allowed transitions in the dimer, which are
10570 J. Phys. Chem. A, Vol. 114, No. 39, 2010 Kahan et al.

SCHEME 2: Schematic Orbital Energy Level Diagram

Left and right: the calculated orbital energies (Hartrees) of the dominant orbitals involved in the monomer and the S0-S1 and S0-S3 transitions.
Orbital shapes shown on left. Middle: the new orbitals of dimer4, B3LYP/6-31G(d). The nearly degenerate orbitals 99 and 100 are type (ii) orbitals
related to orbital 50 of the monomer, 101-102 are type (ii) orbitals related to orbital 51 of the monomer and 103-104 are combination and
anti-combination (type (i)) from orbital 52 in the monomer. The transitions originating in type (ii) orbitals split to allowed and less allowed transitions
in the dimer. The allowed and less allowed transitions are 600-800 cm-1apart. Transition S0-S1 (a), S0-S1 (b), S0-S3 (a), and S0-S3 (b) have
partial CT character.

separated by 600-800 cm-1 in dimer4. In other dimer structures

the shift between the allowed and less allowed transitions was
found to vary between 300 and 3300 cm-1, depending on the
geometry. CT and ππ* transitions (though not necessarily both
of them) were also found in these structures. The transitions’
character was found to be functional dependent. For further
details see Table S5 and S6.
Most of the calculated dimer transitions yield an allowed
transition that is blue-shifted with respect to the relevant
monomer transition according to both TDDFT methods. In
Figure 7, the monomer transitions are shown in black squares,
and other relative transitions of all calculated dimer structures
are shown by other black-gray symbols. For the B3LYP
calculations two trimers structures were also calculated, in
addition to dimer1 and dimer2, and transitions of trimer2 are
also shown in Figure 7. The calculated transitions must be
shifted by -7300 cm-1 (7200 cm-1) for B3LYP (BNL) in order Figure 7. The calculated oscillator strengths of electronic transitions
to coincide with the experimental ones (this shift was determined of the IDP monomer, dimer2 and trimer3 structures (See Table 2).
by the 490 nm band of the monomer experimental excitation Black: TDDFT/B3LYP/6-31G(d) level calculations, shifted by -7300
spectra). Figure 7 compares the experimental electronic spectra cm-1. Squares: monomer, circles: dimer2, triangles: trimer2. Gray:
of the dimer and the monomer with the calculated ones and TDDFT/BNL/6-31G(d) level calculations shifted by -7200 cm-1,
their oscillator strengths using the two functionals for dimer2. squares: monomer, circles: dimer2; compared to the experimental
monomer (black line) and dimer spectra (gray dashed).
The calculated transitions of the other structures can be seen in
detail in Tables S4 and S5. The calculated S0-S1 and S0-S3 505 nm, in addition dimer2 upon using the B3LYP functional,
(S2) transitions of the monomer were found to reproduce the was found in the calculation of dimer1 using BNL and in dimer4
monomer experimental absorption spectrum. The agreement structure using the B3LYP functional. Trimer1 and trimer2 (See
between the experimental dimer bands and the calculated ones Scheme S1 in the Supporting Information) also contribute to
is much poorer. The narrow red-shifted band at 505 nm appears the 505 nm band. A contribution to the blue side comes from
weakly by B3LYP calculations, and the broad blue-shifted band all other calculated dimers using both functionals, but again none
is also reproduced by B3LYP calculations, but with a smaller of the calculated transitions of the dimer reproduces quantita-
shift. In addition, no broadening mechanism that can predict tively the total dimer bands.
the large width of the band of only a single transition could be Using the DHO model for the monomer absorption spectra
simulated. A certain contribution to the experimental band at at 83 and 298 K we separated the two main contributions to
Photophysics of a Polar Molecule in a Nonpolar Glass
the absorption band, S0-S1 and S0-S3. The oscillator strength
for S0-S1 was calculated to be 0.28 and for S0-S3 to be 0.25
(See Figure S2 and Table S1 for fitting details). These results
are somewhat different from those reported in ref 1, but since
they were obtained upon iterating between two temperatures,
RT and 83 K, we consider the present ones as more reliable.
Discussion
In view of the presence of the dimer in the cryogenic glass
(at least in the case of MCHIP), the previous kinetic scheme
(ref 1) is now modified as follows:
M(S0) + hν f M(S*) (6)
2M(S0) a D(S0) Keq Dimer formation (7)
D(S0) + hν f D(S*) (8)
M(S*) f M(S0)) + hν k0f M fluorescence (9)
M(S*) f M(S0) kIC M internal conversion (10)
D(S*) f D(S0)) + hν′ k′0
f D fluorescence (11)
D(S*) f D(S0) ′ D internal conversion
kIC (12)
Formation of the triplet state is ignored since no evidence for
phosphorescence was observed experimentally.
It was shown earlier1 that in fluid nonpolar solvents internal
conversion is very efficient due to the presence of a CI that
causes a very rapid decay to the ground state, on time scale of
hundreds of femtoseconds. The decay is faster in nonpolar
solvents than in polar ones. Since now we have the full
characteristic of the fluorescence and absorptions in the nonpolar
solvent, we can try to re-evaluate kf, the measured radiative rate
constant. Since the electronic absorption spectrum of the BIDP
monomer actually consists of two overlapping bands, assigned
to the S0-S1 and S0-S3 transitions, the DHO model was used
to evaluate (by eq 5) that at 83 K the pure radiative lifetime of
S1 is kf0 ) 1.4 × 108 s-1. kf, which is defined by eq 13,
kf ) k0f + kIC (13)
is related to kf0 by the monomer quantum yield (φ(0)) by:
φ(0) ) k0f /kf (14)
where (φ(0) signifies the quantum yield in the absence of self-
quenching). Using low concentration solutions, in which the
dimer concentration can be neglected, the fluorescence quantum
yield is 0.9, and thus kf ) 1.6 × 108 s-1, replacing the results
presented in ref 1. At room temperature fluorescence in MCHIP
is below the noise level, leading to an upper limit for the
quantum yield of about 4 × 10-5, 1 order of magnitude less
than in acetonitrile, (4 × 10-4). Thus, at 298 K a lower limit
for kf is1.4 × 108/4 × 10-5 ) 3.5 × 1012 s-1. This large value
is due primarily to kIC, which is estimated to be kIC = 1012 s-1,
J. Phys. Chem. A, Vol. 114, No. 39, 2010 10571
showing that internal conversion is the dominant process in
MCHIP at room temperature.
It is evident that the fluorescence yield increases dramatically
as the temperature is decreased to less than 143 K (Figure S3).
This temperature is close to the reported melting point of the
mixture, 147 K,30 and strengthens the assumption that the
increased viscosity at the cryogenic temperatures inhibits BIDP
from reaching the geometry of the CI, a 90° torsion angle
between the two rings, and therefore increases the efficiency of
the fluorescence. As shown in Figure S3, Fluorescence is
completely quenched at 143 K, a temperature at which dimer-
ization is quite extensive (essentially complete). At lower
temperatures, fluorescence increases, as expected for increased
rigidity of the solvent. Thus, we surmise that the main effect of
the cooling is due to the hindrance of the torsion in the
monomer. At these lower temperatures the dimer concentration
is large yet fluorescence is quite strong. Thus, the main effect
of cooling is the prevention of access to the conical intersection.
From the analysis we derived Keq )(4 ( 3) × 105 M-1, a
value similar to that obtained for other systems such as dyes in
nonpolar solvents.31 This is in line with a strong dipole-dipole
interaction that in nonpolar solvents and leads to more extensive
dimerization than in polar solvents. The blue shift of the dimer
is 4000 cm-1, the upper limit of the shifts between the monomers
and dimers for the above-mentioned dyes.31 The derived Keq is
also of the same order as that reported for merocyanine dimers
that are mainly H-aggregates (blue-shifted) and strongly
quenched.32
The quenching process is analyzed by Stern-Volmer equa-
tion, yielding KSV ) (1.5 ( 0.1) × 106 M-1. Since KSV is much
larger than expected for dynamic quenching,13 and since
dynamic quenching is not likely to be important in cryogenic
glasses, static quenching is proposed as the main process. We
adopt the “dark complex model” offered by Boaz and Rollef-
son,33 which suggests that the quenching is caused by a new
ground state complex, whose fluorescence quantum yield is
lower. The model also suggests that the complex constituents
interact by van der Waals forces, in agreement with the value
of 4 Å calculated for the distance between the components of
the stable complex. (See also ref 34 and the QM calculation).
In most static quenching models, KSV should be very similar to
Keq, but according to our analysis it is four times larger. There
is a likelihood of efficient energy transfer from the monomer
to the dimer that can apparently increase KSV. Another possible
effect is the creation of an inhomogeneous concentration
distribution in the high-viscosity solvent, due to the tendency
of BIDP molecules to be closer to one another and create sites
of dimerization. In such situations the effective concentra-
tion of BIDP is higher than the average one, leading to
apparently more efficient quenching.
The temperature dependence (Figure 1) of BIDP absorbance
can be used to analyze at what temperature and how the dimers
are formed. Two critical temperatures, T1 ) 147 K and T2 )
200 K appear to arise from the data. Similar values were noted
by other experimental papers, such as Mandanici et al.,35 Angell
et al.,36 and Abramczyk et al.,37,38 who assigned the lower one
melting point and the higher one to a change from the liquid
phase to a premelting structure, which affects the vibrational
dynamics of MCH. These temperatures match our experimental
data. The overall decrease of the absorbance as the system
cooled to about 200 K can be explained by the dimer formation
and the change in the molar absorption coefficient of the
monomer. (The absorption of all components appears to
decrease, note that the spectra were rescaled to the volume
10572 J. Phys. Chem. A, Vol. 114, No. 39, 2010
TABLE 3: Summary of the Important Constants Evaluated in This Work
units

, dielectric constant, 83 K
melting point/glass point °K

, extinction coefficient cm-1 M-1
λmax, 83 K
fS0-S1, 83 K
fS0-S3, 83 K
fS0-S1, TDDFT/B3LYP
fS0-S3, TDDFT/B3LYP
kf0, (A01)c 83 K s-1
τ0)1/ kf0, c 83 K ns
a
Φfl, 83 K
KISC + kIC, 83 K using Φfl ) s-1
kfl/(kfl + kISC + kIC)
Φfl, RT
kf ()kIC) s-1
τf fs
Κeq, 83 K M-1
Κsv, 83 K M-1
∆Η kcal/mol
a
Fluorescence quantum yield compared to Coumarine 540. b from ref 30. c Evaluated using DHO model and Strickler-Berg equation. d The
range for different dimer structures.
change). For concentrations from 7.4 × 10-6 to 5.0 × 10-5 M
the spectra were reconstructed by using the line shape, the cell
length, concentrations, and molar absorption coefficients of the
monomer and dimer, respectively
Using the DHO model and the resulting separation between
the monomer and the dimer at different temperature led to two
results. First, it is clear that the two bands of the dimer appear
together (Figure 5a), a fact that was not clear from raw data.
The second result is the Van’t Hoff analysis, which apparently
results in two slopes. In the range 298-198 K, ∆Hdim ) 7 ( 2
kcal/mol is extracted from the data; this value is in very good
agreement to the calculated results for ∆E (Table 1, dimer4);
The agreement is reasonable in this case as the volume change
is small. The resulting magnitude is similar to other molecules
such as cyanines (10-17 kcal/mol).39 At lower temperatures
the slope is very small. It appears that the dimerization processes
proceeds to equilibrium as long as the solvent is fluid, and once
the solvent is frozen, further changes in spectrum are mainly
due to changes in the line shapes of the monomer and dimer
spectra and not to changes in their relative concentrations. It is
realistic to expect two regions since in the higher temperatures
range no solidification of the solvent occurs and dimerization
can be take place, whereas in the lower temperatures region
the relative motion of monomer molecules is inhibited.
It is instructive to compare our results with Kasha’s exciton
model in which a structure wherein the two transition dipoles
of the monomers are parallel produces two new excited states
of which the blue-shifted state is allowed. An allowed excited
state that is red-shifted with respect to the monomer appears
for a dimer structure in which the two transition dipoles are
in-line. A splitting yielding two allowed transitions occurs at
oblique transition moments. Kasha’s model predicts for van der
Waals dimers 1000-2500 cm-1 blue shift compared to the
monomer, followed by fluorescence quenching. In our case a
splitting to the red and to the blue was found, wherein the shift
to the blue is larger than the Kasha model prediction. Since
according to the Kasha exciton model the dimer’s structure is
reflected in the resulting dimer absorption spectrum one can
try to find if there is a preferred dimer structure of the BIDP.
The two new excited states predicted by the model are clearly
revealed in the QM calculations, as Scheme 2 shows for dimer4.
Kahan et al.
MCHIP
1.53b
146b
monomer dimer
30 000 ( 3000 21 000 ( 2000
@457 nm @390 nm
0.28c
0.25c
0.49 0.3-0.5d
0.21 0.6-0.9d
1.4 × 108
7
83K
0.9 at [M]corr ) 7.2 × 10-6 M
1.6 × 108
e10-5
3.5 × 1012
290
(4 ( 3) × 105
(1.5 ( 0.1) × 106
7(2
Every two monomer orbitals create two dimer orbitals, that
contribute to electronically excited states that are red or blue-
shifted with respect to the monomer excited state. The optical
transition to one of these is more allowed than to the other. In
most of the structuressKasha’s in-line, parallel, and otherssthe
allowed transitions are blue-shifted compare to the same
transition of the monomer. Only in two cases, dimer transitions
were found to be allowed red-shifted transitions: the S0-S3
transition in dimer1, Kasha’s in line dimer, at the B3LYP level,
and the S0-S1 transition in dimer1 at the BNL level. Therefore,
the prediction made by Kasha that the structure is responsible
for the red/blue shift is partly confirmed in the QM methods.
The splittings calculated between the monomer and the dimer
are in the range of 300-3300 cm-1, similar to the Kasha model
estimates.
Two types of dimer transitions, CT transitions and ππ*, can
be discerned in the dimers; they may be rationalized by the
nature of the dimer’s MOs. In some dimers the electronic
distribution is spread over the entire structure, and in others it
is found only on one monomer. Whereas the CT-type transitions
are blue-shifted only, ππ* transitions can be red or blue-shifted
(See Tables S5 and S6 for detailed information). DFT/BNL
calculations are expected to yield better agreement with experi-
ment for CT states,21 but in the present case a shift of -7300
cm-1 (-7200 cm-1) was needed in the case of both functionals
for agreeing with experiment (monomer). Similar differences
between experiments and TDDFT calculated transition energies
where reported,40,41 and since we are interested in exploring the
transition behavior upon dimerization and not the absolute
numbers, no other action was needed except a linear correction.
Even upon applying the correction, the agreement between the
calculated spectra to the experimental is rather limited. The large
blue shifted band is not reproduced in the calculations (Figure
7), and attempts to include homogeneous and in-homogeneous
line width factors, using the DHO model, were not successful
in predicting the experimental line shape. It might be that there
is a special structure that produces this spectrum or some local
effects that shift the spectrum. Since the red and the blue bands
change similarly upon cooling they must arise from a single
process of formation. The trimer calculations offered by B3LYP
functional, which show less stable structures, contribute to the
Photophysics of a Polar Molecule in a Nonpolar Glass
line shape only marginally on the red side, but contributions
from larger aggregates cannot be ruled out completely. An effort
to perform DHO simulations for the dimer line shape or for the
total band line shape at 83 K with respect to the calculated
transitions did not succeed; it was especially hard to reproduce
the large broadening of the blue-shifted band. Similarly large
shifts were recorded for dimers bonded by a hydrogen bond,40
but in our case they can be ruled out.
It is concluded that the computational methods used reproduce
qualitatively the red and blue-shifted bands of the exciton model,
but quantitative agreement was not obtained.
Conclusions
In this work it is shown that the low temperature absorption
of BIDP in nonpolar glasses can be quantitatively understood
if dimer formation is considered. Table 3 summarizes the
important physical constants obtained in this work. Analysis of
the spectra at different concentrations and a careful separation
between the contributions of the dimer and monomer lead us
to the determination of Keq at 83 K. Dimer formation is also
accompanied by monomer fluorescence quenching, with KSV
)(1.5 ( 0.1) × 106 M-1, assigned to static quenching.
The low temperature monomer absorption line-shape allows
us to make a new DHO fit and to improve our previous estimate
of the fluorescence efficiently of the monomer. Working under
conditions of negligible dimerization, internal conversion is
dominant in fluid solutions (kIC = 1012 s-1, compared to kf ≈
108 s-1), whereas in the glassy solvent at 83 K the nonradiative
process is 10 times slower than the radiative one.
The dimer line shape, which consists of a narrow red-shifted
band and broad blue-shifted one, is in qualitative agreement
with Kasha’s exciton model. QM calculations at the DFT level
were found to predict the two new optically allowed transitions
to excited states of the dimer. The two monomer MOs that
chiefly contribute to these dimer states interacting with each
other were identified. The ability to predict the dimer spectrum
from the QM calculation is very limited.
The temperature dependent measurements and the DHO
analysis indicate the existence of two temperature regimes, in
agreement with the solidification and crystallization process of
MCHIP.37 In the higher temperature range (195-298 K)
dimerization takes place with an enthalpy of formation, ∆Hdim
) 7 ( 2 kcal/mol, in agreement with theoretical estimates. It is
also found that the red and blue-shifted bands appear and change
similarly as a function of temperature. This indicates that the
dimerization process takes place before crystallization and
creates simultaneously the blue and the red-shifted bands in the
spectrum. The DHO model was found to be a useful and reliable
tool for the monomer absorption at all temperatures, but not
for the dimer.
The dimerization process occurs mainly in the temperature
range between 298 and 195 K. Upon further cooling to 83 K
crystallization of the solvent sets in and inhibits free movement
of the solute. This prevents further dimerization on one hand,
and in addition hinders the torsional motion of the monomer,
which is required in order to reach to the geometry of conical
interaction, making the fluorescence process more efficient then
the IC. The new analysis corrects τf to be 2.9 × 10-13 s, smaller
than in polar solvent shown in ref 1, strengthening the main
assumption that in nonpolar solvent internal conversion via the
CI is more efficient.
Acknowledgment. A. K. thanks the Ministry of Science and
Technology, for a Levi Eshkol Ph.D. Scholarship. The Minerva
J. Phys. Chem. A, Vol. 114, No. 39, 2010 10573
Farkas Center for Light Induced Processes is supported by the
Minerva Gesellschaft mbH. We are grateful to Prof. Roie Bear’s
group and especially to Mrs. Tamar Stein, for discussion of the
BNL functional and for the BNL tuning.
Supporting Information Available: Experimental spectra
of BIDP, tables of experimental parameters and results, and
schemes of the monomers, dimers, and trimers. This material
is available free of charge via the Internet at http://pubs.acs.org.
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