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Resonance Raman spectroscopy of the S 1 and S 2 states of pyrazine:

Experiment and first principles calculation of spectra
Gerhard Stock, Clemens Woywod, and Wolfgang Domcke
Institute of Physical and Theoretical Chemistry, Technical University of Munich, D-85748 Garching,
Germany
Tim Swinneya) and Bruce S. Hudson
Department of Chemistry and Chemical Physics Institute, University of Oregon, Eugene, Oregon 97403
~Received 23 June 1995; accepted 20 July 1995!
New experimental and theoretical data on the resonance Raman ~RR! spectroscopy of the S 1 and S 2
states of pyrazine are presented. Based on recent ab initio CASSCF ~complete-
active-space-self-consistent-field! and MRCI ~multireference configuration interaction! calculations
of Woywod et al. @J. Chem. Phys. 100, 1400 ~1994!#, we construct a vibronic coupling model of the
conically intersecting S 1 and S 2 states of pyrazine, which includes the seven most relevant
vibrational degrees of freedom of the molecule. Employing a time-dependent approach that treats
the intramolecular couplings in a nonperturbative manner, we calculate RR cross sections for this
model, taking explicitly into account the nonseparability of all vibrational modes. The combination
of high-level ab initio calculations and multimode propagation techniques makes it possible, for the
first time, to make first-principles predictions of RR spectra for vibronically coupled electronic
states of an aromatic molecule. The theoretical data are compared to experimental gas-phase RR
spectra which have been obtained for five different excitation wavelengths. The comparison reveals
that the ab initio predictions match the experimental results in almost every detail. 1995
American Institute of Physics.

I. INTRODUCTION shifts are inferred from experimental data.11,12 Only few

The photophysics and photochemistry of excited singlet
states of simple aromatic molecules have attracted consider-
able interest over the past few decades.1,2 While the spectros-
copy of low vibronic levels of the first singlet state ~S 1! is
well established, in particular for representative simple sys-
tems such as benzene and pyrazine ~see, for example, Refs.
39!, very little is still known about the photophysical dy-
namics of the S 2 state and higher excited singlet states. The
spectroscopic investigation of these states is often hampered
by large line broadening of the electronic spectra, rendering
the appearance of the absorption and fluorescence bands
typically diffuse and rather structureless.
Besides time-resolved techniques, which are about to be-
come available due to recent development of uv femtosecond
laser sources,10 resonance Raman ~RR! spectroscopy has
proven to be very useful to obtain specific information on the
vibrational and relaxational dynamics of short-lived higher
singlet states.1114 Even in the case of structureless absorp-
tion bands, RR spectra can yield valuable knowledge of the
symmetries and geometries of excited states, the location of
optically forbidden transitions, and the shapes of excited-
state potential-energy surfaces ~PESs! along displaced
modes.1114 Theoretical investigations of RR processes have
employed either the time-independent15 or the
time-dependent16 formulation of RR spectroscopy. The usual
approach to simulate RR spectra is to assume a separable
harmonic model for both ground and excited electronic
states, whereby the vibrational frequencies and geometry
a!
Current address: Stanford Research Systems, 1290 D Reamwood Ave.,
Sunnyvale, CA 94089.
workers have performed ab initio calculations at the
HartreeFock level, which allow to roughly estimate the ge-
ometry changes in the excited states.17,18
The S 1 [ 1 B 3u (n p * )] and S 2 [ 1 B 2u ( pp * )] excited states
of pyrazine represent a classic example of vibronic coupling
in aromatic systems. For symmetry reasons, the out-of-plane
deformation mode n 10a (B 1g ) is the single normal mode of
pyrazine which can couple the 1B 3u and 1B 2u states in first
order. Manifestations of the vibronic activity of n10a have
been observed in the absorption spectrum, in single-vibronic-
level fluorescence spectra, and in RR spectra of the S 1
state.59,19,20 The S 1 2S 2 vibronic coupling furthermore
causes an ultrafast S 2 S 1 internal conversion process as has
been discussed in detail in Ref. 21.
A considerable amount of theoretical investigations has
been concerned with the S 1 2S 2 vibronic-coupling problem
in pyrazine; see Ref. 9 for a comprehensive list of citations
up to 1988. More recently, calculations of the RR and fluo-
rescence spectra22,23 and the simulation of femtosecond
pumpprobe experiments, considering transient absorption24
as well as two-photon ionization signals25 have been re-
ported. In particular, a series of electronic structure calcula-
tions of increasing accuracy ~with respect to the treatment of
electron correlation! and completeness ~with respect to the
vibrational modes considered! have been performed,23,26,27
which have identified a conical intersection28 of the S 1 and
S 2 adiabatic PESs within the FranckCondon region. Most
recently, the conically intersecting S 1 and S 2 PESs have been
characterized by CASSCF ~complete-active-space-self-
consistent field!/MRCI ~multireference configuration interac-
tion! calculations.26,27

J. Chem. Phys. 103 (16), 22 October 1995 0021-9606/95/103(16)/6851/10/$6.00 1995 American Institute of Physics 6851
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6852 Stock et al.: Raman spectroscopy of pyrazine
In this work we present new experimental and theoreti-
cal data on the RR spectroscopy of the S 1 and the S 2 states of
pyrazine. While Raman spectra resonant to the S 1 (n p * )
state of pyrazine have been reported for excitations at several
wavelengths,19,20 only a single S 2 RR spectrum ~at 266 nm!
is available in the literature.20 Here, we report gas-phase RR
spectra of pyrazine for five excitation wavelengths within the
S 2 absorption band. These experimental data are compared
with ab initio calculations of RR spectra. To obtain these
spectra, we have extended the calculations of Ref. 27 to ob-
tain the complete set of parameters of the Taylor expansion
~gradients and Hessian matrices! of the S 1 and S 2 surfaces at
the S 0 equilibrium geometry. Based on the ab initio data we
have constructed a vibronic-coupling model including seven
nonseparable vibrational modes. For this model, RR cross
sections have been obtained in a time-dependent approach,
treating the intramolecular coupling in a nonperturbative
manner. Apart from the electronic S 1 2S 2 gap, which had to
be adjusted by less than 2%, and a phenomenological line-
width, which was inferred from the experimental absorption
spectrum, we have used exclusively ab initio data for the
calculation of the RR spectra. The comparison of the theo-
retical predictions with the new experimental gas-phase RR
spectra obtained at five excitation wavelengths provides a
stringent test of the theoretical model.
II. AB INITIO CALCULATIONS
A. Methods
Our aim is the characterization of the multidimensional
PESs of the S 1 (n p * ) and S 2~pp*! of pyrazine within the
range of nuclear coordinates which is relevant for the calcu-
lation of absorption and RR spectra. In previous works, the
S 1 and S 2 PESs have been characterized within the subspace
of the five totally symmetric normal modes n1 , n2 , n6a , n8a ,
n9a and the S 1 2S 2 coupling mode n10a of B 1g symmetry by
the calculation of one-dimensional cuts along normal coordi-
nates and two-dimensional surface calculations in selected
subspaces.23,27 We have now extended these calculations to
obtain the complete set of parameters of the Taylor expan-
sion ~gradients and Hessian matrices! of the S 1 and S 2 sur-
faces at the S 0 equilibrium geometry.
The S 0 equilibrium geometry has been optimized at the
MP2 level ~second-order Mo llerPlesset perturbation theory!
using the Cambridge Analytic Derivatives package
~CADPAC!.29 A double-zeta basis set with polarization func-
tions on all atoms ~DZP!30 has been employed. For the S 0
surface in the vicinity of the equilibrium geometry, the MP2
treatment is adequate and has been shown to yield rather
accurate geometry parameters and vibrational frequencies for
pyrazine.23,31 The molecule is taken to lie in the y z plane,
with the z axis going through the nitrogen atoms.
The S 0 harmonic force field in Cartesian coordinates has
been obtained at the MP2 level and diagonalized to yield the
normal coordinates and harmonic vibrational frequencies of
pyrazine.
We have employed the CASSCF method32 for the calcu-
lation of the S 1 and S 2 PESs of pyrazine. The CASSCF ap-
proach properly accounts for quasidegeneracy effects, which
J. Chem. Phys., Vol. 103, No. 16, 22 October 1995
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is essential for the correct description of multidimensional
surface crossings.32 A detailed description of these calcula-
tions for pyrazine has been given previously.27 The active
space consists of six valence p orbitals ~three of which are
occupied in the ground-state SCF configuration! as well as
the two nonbonding orbitals on the nitrogens. The CASSCF
calculation thus distributes ten electrons over eight orbitals.
To obtain a balanced description of the S 0 , S 1 , and S 2 sur-
faces, all three states have been included in the CASSCF
functional with equal weight. The state-averaged CASSCF
calculation defines a single set of orbitals for the three lowest
singlet states, which simplifies the calculation of transition-
dipole-moment functions. The CASSCF calculations have
been performed with the program system MOLPRO33 employ-
ing a DZP basis set.34
Electron-vibrational coupling constants have been calcu-
lated as derivatives of electronic excitation energies with re-
spect to ground-state normal coordinates. The coupling con-
stants are defined as35
S D
]Ek
k ~i k ! 5 , ~1!
]Qi 0
S D
1 ] 2E k
g ~i kj ! 5 , ~2!
2 ] Q i] Q j 0
where E k denotes the electronic excitation energy and the Q i
are dimensionless normal coordinates. The k(k) i and gi j have
(k)
been evaluated by numerical differentiation at the CASSCF
level. The k(k) are nonzero only for the five totally symmet-
i
ric modes of pyrazine, while the g(k) i j are nonzero for all
vibrational modes. The off-diagonal coupling constants g(k) ij ,
which are responsible for the Dushinsky rotation36 of normal
coordinates, are nonzero only for modes belonging to the
same symmetry species in the D 2h point group.
The mode n10a of B 1g symmetry is responsible for
S 1 2S 2 vibronic coupling and requires a special treatment. In
Ref. 27 a diabatic electronic representation37 has explicitly
been constructed. The vibronic-coupling constants l is then
defined as the first derivative of the off-diagonal element of
the electronic Hamiltonian, and g(k) 10a,10a as the second de-
rivative of the diagonal elements with respect to Q 10a . We
refer to Ref. 27 for details.
B. Results
The harmonic vibrational frequencies of pyrazine ob-
tained at the MP2 level with the DZP basis set are listed in
Table I. They may be compared with experimental funda-
mental frequencies, which have been compiled in Ref. 9.
With the exception of CH stretch modes, for which anhar-
monic corrections are significant, the agreement is very
good. This gives us confidence that the ground-state normal
coordinates are reliably described at the MP2 level. MP2
harmonic frequencies of pyrazine have also been obtained by
Zhu and Johnson, employing a slightly smaller basis set.31
The present results are in better overall agreement with the
experimental data.
The linear coupling constants k(k) i for the five totally
symmetric modes n1 ,n2 ,n 6a , n 8a , n 9a have been calculated in
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Stock et al.: Raman spectroscopy of pyrazine 6853

TABLE I. Harmonic vibrational frequencies ~in cm21! of the 1A g ground the S 1 state and the modes n14 , n17a , n4 , and n5 in the S 2
state of pyrazine. Theoretical frequencies are given both at the MP2 and state. Significant off-diagonal quadratic coupling constants,
CASSCF levels of theory and are compared with experimental fundamental
leading to Dushinsky rotation of the normal modes, are
frequencies ~Ref. 9!.
found in B 1u symmetry ~n12 ,n 18a , n 19a ,n13!, B 3g symmetry
Symmetry Mode Experiment MP2 CASSCF ~n3 ,n8b ! and A u symmetry ( n 16a , n 17a ) in the S 1 state; in the
S 2 state, significant off-diagonal quadratic couplings are
Ag n6a 596 597 672
n1 1015 1027 1072 found in B 2u symmetry ~n14 ,n19b ! and B 1u symmetry
n9a 1230 1264 1347 ~n12 ,n18a !.
n8a 1582 1633 1797 By determining the gi j at the CASSCF level, we have
n2 3055 3280 3329 neglected dynamic electron correlation effects; by determin-
B 1g n10a 919 914 970 ing vi at the MP2 level, on the other hand, dynamic corre-
lation effects have been accounted for. It is thus not fully
B 2g n4 756 761 774
consistent to combine the CASSCF quadratic coupling con-
n5 983 913 1039
stants with the MP2 ground-state frequencies in the construc-
B 3g n6b 704 711 774 tion of the model Hamiltonian. To correct for the uneven
n3 1346 1384 1509 treatment of ground and excited states, we define scaled qua-
n8b 1525 1592 1649
n7b 3040 3254 3307
dratic coupling constants g 8i j according to

Au n16a 341 343 434 g 8i j 5X i g i j X j , ~3!

n17a 960 900 1069
where
B 1u n12 1021 1032 1251
n18a 1136 1166 1248 X i 5 @ v i ~ MP2 ! / v i ~ CASSCF!# 1/2 . ~4!
n19a 1416 1456 1680
n13 3012 3253 3312 The ground-state vibrational frequencies obtained at the
B 2u n18b 1063 1092 1177
CASSCF level have been included in Table I; the scaling
n14 1149 1369 937 factors X i can thus be taken from this table.
n19b 1416 1456 1522 The results collected in Tables IIII provide the quanti-
n20b 3063 3277 3320 tative basis for the construction of model Hamiltonians
B 3u n16b 420 426 468 which systematically include all vibrational modes which
n11 785 781 850 couple significantly to the S 0S 1 and S 0S 2 electronic
transitions in pyrazine.

Ref. 27 at the CASSCF and MRCI levels. These data are

reproduced in Table II for completeness. It can be seen from
Table II that dynamical correlation effects are not of decisive
importance for the energy gradients.
In Ref. 27 the linear vibronic coupling constant l as well
as the quadratic coupling constants g(k)
10a,10a have been ob-
tained at the CASSCF and MRCI levels. The results are
~MRCI values in parentheses!: l50.1676 eV ~0.1825 eV!
and g (1)
10a,10a 5 g 10a,10a 520.0180 eV ~20.0180 eV!. The
(2)
III. CALCULATION OF RESONANCE-RAMAN
SPECTRA
A. Model Hamiltonian
For the calculation of optical spectra of vibronically
coupled electronic states it is advantageous to formulate the
model Hamiltonian in a diabatic electronic representation,37
which has explicitly been constructed in Ref. 27. Let uw0&

relatively large negative value of g10a,10a implies a signifi-
cant reduction of the vibrational frequency of g10a in both
excited states.
The quadratic coupling constants for all other modes of
pyrazine obtained at the CASSCF level are collected in Table
III. Significant quadratic couplings ~i.e., large diagonal ele-
ments gii ! are found for the modes n12 ,n 8b , n 17a , n 18a ,n14 in
TABLE II. Gradients of the excitation energies of the S 1 and S 2 states of
pyrazine with respect to dimensionless totally symmetric normal coordinates
obtained at the CASSCF and MRCI levels of theory. Units are eV.
Q1 Q2 Q 6a Q 8a Q 9a
denote the electronic ground state and uw1& and uw2& denote
the S 1 (n p * ) and the S 2~pp*! state, respectively. Similar to
previous work, we treat the strong vibronic S 1 2S 2 coupling
via the mode n10a exactly to all orders, whereas the intramo-
lecular coupling of the excited electronic states uw1&, uw2&
with the well-separated electronic ground state uw0& is ne-
glected. As has been found in experimental investigations,38
the S 1,2 S 0 internal conversion process takes place on a
picosecond time scale, and can therefore be ignored, as well
as intersystem crossing, on the femtosecond timescale of RR
spectroscopy. Neglecting furthermore vibronic couplings and
possible intersections of S 1 and S 2 with higher singlet states,
the model Hamiltonian reads

k~1! 20.0808 20.0938

(
CASSCF 0.0281 0.0193 0.1511
k~2! 20.2234 0.0340 0.1029 0.0248 0.0509 H5 u w k & h k ^ w k u 1 $ u w 1 & V 12 ^ w 2 u 1H.c.% . ~5!
k50,1,2
MRCI k~1! 20.0470 0.0368 20.0964 20.0623 0.1594
k~2! 20.2012 0.0211 0.1193 0.0348 0.0484 The vibrational dynamics in the electronic ground state
is described by the harmonic-oscillator Hamiltonian h 0

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6854 Stock et al.: Raman spectroscopy of pyrazine

TABLE III. The quadratic coupling constants g ~1! and g ~2! ~in eV! of the S 1 and S 2 PE functions of pyrazine obtained at the CASSCF level.

A g modes (D 2h D 2h )
Symmetry Mode Q1 Q2 Q 6a Q 8a Q 9a
(B 3u )S 1 Q1 20.000 46 0.000 25 20.001 59 20.000 92 0.000 12
Q2 0.000 14 20.000 29 0.003 70 20.002 75
Q 6a 0.001 92 0.002 63 0.001 17
Q 8a 20.011 94 0.003 60
Q 9a 20.003 73
(B 2u )S 2 Q1 0.002 76 0.000 93 20.004 37 20.001 03 0.001 00
Q2 20.000 49 0.000 86 20.000 24 20.000 51
Q 6a 20.006 73 0.000 30 0.002 07
Q 8a 0.008 85 0.001 73
Q 9a 0.002 67
A u modes (D 2h D 2)
Symmetry Mode Q 16a Q 17a
(B 1 )S 1 Q 16a 0.014 57 20.012 15
Q 17a 20.047 08
(B 2 )S 2 Q 16a 20.018 56 0.000 07
Q 17a 20.064 54
B 1g mode (D 2h C 2h )
Symmetry Mode Q 10a
(B u )S 1 Q 10a 20.018 00
(B u )S 2 Q 10a 20.018 00
B 2g modes (D 2h C 2h )
Symmetry Mode Q4 Q5
(B g )S 1 Q4 20.023 06 20.003 57
Q5 20.012 60
(A u )S 2 Q4 20.035 28 0.007 00
Q5 20.036 10
B 3g modes (D 2h C 2h )
Symmetry Mode Q 6b Q3 Q 8b Q 7b
(A u )S 1 Q 6b 20.005 99 0.000 24 0.005 60 20.001 25
Q3 20.008 01 20.012 50 0.004 00
Q 8b 20.051 57 0.006 65
Q 7b 20.000 13
(B u )S 2 Q 6b 20.010 79 20.000 11 20.000 47 0.000 45
Q3 20.008 16 0.000 68 20.000 26
Q 8b 0.006 61 20.000 70
Q 7b 20.009 52
B 1u modes (D 2h C 2v)
Symmetry Mode Q 12 Q 18a Q 19a Q 13
(B 1 )S 1 Q 12 20.076 72 20.037 15 0.021 60 20.010 20
Q 18a 20.032 68 0.016 75 20.009 30
Q 19a 20.014 10 0.002 15
Q 13 20.001 28
(B 2 )S 2 Q 12 20.009 97 0.010 10 20.005 55 0.002 87
Q 18a 20.013 02 0.006 30 20.000 14
Q 19a 20.013 52 0.000 58
Q 13 20.009 39
B 2u modes (D 2h C 2v)
Symmetry Mode Q 18b Q 14 Q 19b Q 20b
(B 1 )S 1 Q 18b 20.003 07 0.000 15 0.001 89 20.001 45
Q 14 0.031 99 20.000 92 20.000 53
Q 19b 20.006 20 20.004 50
Q 20b 0.000 74
(A 1 )S 2 Q 18b 20.013 05 20.008 40 0.003 16 0.001 44
Q 14 0.107 78 0.037 50 0.000 68
Q 19b 0.008 41 20.000 95
Q 20b 20.009 52
B 3u modes (D 2h C 2v)
Symmetry Mode Q 16b Q 11
(A 1 )S 1 Q 16b 20.014 74 0.006 00
Q 11 20.010 54
(B 2 )S 2 Q 16b 20.015 07 0.006 00
Q 11 20.016 92

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Stock et al.: Raman spectroscopy of pyrazine 6855

h 05 (i
vi
2 S
2
]2
] Q 2i
1Q 2i , D ~6!
modes ~n1 , n6a , n8a , n9a !, and two quadratically coupled
modes ~n4 and n14!. The spectroscopic effects of the remain-
ing 17 weakly coupled modes are described in a phenomeno-
where the sum runs over all seven vibrational modes in- logical manner by the dephasing rate 1/T 2 . With the excep-
cluded in the model ~see below!. The diagonal diabatic ma- tion of the vertical S 1 2S 2 energy gap D, which was slightly
trix elements h 1 and h 2 as well as the coupling element V 12 adjusted to reproduce the experimental positions of the two
are expanded in terms of ground-state normal coordinates Q i absorption bands ~from Dab initio50.83 eV27 to Dexp50.846
up to second order, yielding eV!, all vibrational and vibronic coupling constants as well
as vibrational frequencies are taken without any further
h k 5h 0 1E k 1 (i k ~i k !Q i 1 (
i, j
g ~i,kj! Q i Q j , ~7! modification from the ab initio data collected in Tables IIII.

V 12 5lQ 10a . ~8!

B. Calculation of spectra
Here, E k denotes the vertical excitation energy of state uwk &,
The interaction of the molecular system with the radia-
and k(k)
i represents the gradient of the excitation energy with
tion field is given in the dipole approximation by
respect to the totally symmetric coordinate Q i . The g(k) i, j ac-
count for changes in vibrational frequencies and rotations of
the modes in the excited states ~the so-called Dushinsky H 1 ~ t ! 52 (
k51,2
m k0 E ~ t ! 1H.c., ~9!
effect36!.
On the basis of the ab initio data presented above, we are where we have defined
able to specify the vibrational modes Q i which we need to
m k0 5 u w k & emk0 ~ Q! ^ w 0 u , ~10!
include into the model for a successful description of optical
spectra. The vibronic activity of the linearly coupled modes and eE(t) represents the external electric field. The diabatic
is easily estimated by their Poisson parameter ~1/2!k2/v2. It transition-dipole-moment functions mk0 ~Q! have been shown
is clear from previous work that besides the coupling mode to depend only weakly on vibrational coordinates,27 which
n10a at least three totally symmetric modes ~n1 , n6a , n9a ! are allows us to employ the Condon approximation.
indispensable. According to Table II, one should also include In the time-dependent formalism41 43 the absorption
n8a ~because of its considerable gradient k(1)8a in the S 1 state!, cross section is given by
whereas the n2 couplings are seen to be negligible.
( E0 dt e i~ v 1 e !t F kk0 ~ t ! ,
2 a `
The spectroscopic effects of the quadratically coupling s A~ v ! 5 p 2 v 2 Re 0 ~11!
modes can be roughly characterized by their relative fre- 3 e k51,2
quency shifts Dv/v. Table III reveals that the coupling mode where a is the fine structure constant and e0 denotes the
n10a undergoes a considerable frequency shift in the excited energy of the initially populated vibrational ground state. The
states, whereas the quadratic couplings of the totally sym- time-dependent correlation functions
metric modes can be ignored. Table III furthermore shows
F kk 8 2t/T 2
^ vu ^ w 0 u m 0k e 2iHt m k 8 0 u w 0 & u 0&
v ~ t ! 5e ~12!
that from the remaining 18 modes, which couple only in
second order, the modes n4 , n5 , n12 , n14 , n16a , n16b , n17a
exhibit a considerable relative frequency shift in either S 1 or describe the intramolecular excited-state dynamics of the
S 2 . As there is no spectroscopic evidence of n12 and n17a , we system and are obtained by solving the field-free Schro-
have ignored these modes in the present model. From the dinger equation for the model Hamiltonian ~see below!. As
remaining modes which show up at least weakly in the ex- discussed above, the dephasing rate 1/T 2 causes an additional
perimental absorption and emission spectra,59,19,20 we have phenomenological decay of F0(t), resulting in an additional
included the modes n4 and n14 , which are the most important homogeneous broadening of the absorption spectrum.
quadratically coupled modes in the S 1 and the S 2 state, re- In the case of a single optically accessible excited state
spectively. ~say, uw2&!, the RR cross section for orientationally averaged
Although the remaining 17 vibrational modes of pyra- scatterers, integrated over the scattered bandwidth and all
zine do hardly show vibronic activity, they still contribute to scattered directions, can be written as16,22
the overall decay of the electronic polarization ~the so-called
electronic dephasing!, which is reflected, e.g., in the line-
width of the optical absorption spectrum.39 This pure elec-
s v0~ v 1 ! 5
8
9
p 2
a
S D UE
e c
2
v 3s v 1
`

0
dt e i ~ v 1 1 e 0 ! t F 22 U
v ~t! ,
2

tronic dephasing due to the remaining modes is included into
the model in terms of a phenomenological dephasing time
T 2 , which is adjusted to reproduce the homogeneous line-
width of the absorption spectrum of the S 2 state ~T 2535 fs!.
For the S 1 state we introduce T 25400 fs as a purely technical
parameter.40
To summarize, our model of pyrazine incorporates ex-
plicitly seven nonseparable vibrational modes, namely, the
coupling mode n10a , four linearly coupled Condon active
~13!
where uv& represents the final vibrational state, and v1 and vs
denote the frequencies of the laser excitation and the spon-
taneous emission, respectively. In the case that both excited
electronic states carry oscillator strength, interference effects
of the radiation emitted from the two electronic states may
occur, which have to be taken into account when averaging
over the molecular orientations ~see Ref. 44 for a detailed
discussion!.

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6856 Stock et al.: Raman spectroscopy of pyrazine

As described in detail in previous work,21,24 the intramo-

lecular dynamics is treated numerically exactly by solving
the time-dependent Schrodinger equation for the model
Hamiltonian ~5!
]
i u C ~ t ! & 5H u C ~ t ! & . ~14!
]t
The time-dependent state vector is expanded in a direct-
product basis built from diabatic electronic states and
harmonic-oscillator states for each of the seven vibrational
modes. This way Eq. ~4! is converted into a system of first-
order differential equations for the expansion coefficients,
which is solved employing a standard RungeKutta method.
The harmonic-oscillator basis sets for the seven modes have
been truncated at occupation numbers N max 1 59, N 4 54,
max

N 6a 5 18, N 8a 5 4, N 9a 5 7, N 10a 5 15, N 14 5 5, resulting in

max max max max max

a dimension of 1 360 800 of the Hamiltonian matrix for B 2u

and B 3u vibronic symmetries, respectively. The state vector
was propagated up to 2 ps, which took about 12 CPU h on a
Cray YMP for each symmetry. As a check of convergence
and to generate stick spectra for the absorption bands, we
have also employed the Lanczos algorithm,45,46 which al-
lowed us to increase the basis set to include up to 2.5 million
basis states.

IV. EXPERIMENTAL METHODS
The experimental methods used in this work are basi-
cally those described in Ref. 13 except that a CCD multi-
channel detector ~Princeton Instruments! was used. Briefly,
the excitation wavelengths are either harmonics of the
Nd:YAG laser fundamental at 1064 nm or are obtained by
stimulated Raman scattering from one of these harmonics in
hydrogen gas. The vibrational shift in hydrogen gas is 4155
cm21. Anti-Stokes stimulated Raman shifting results in in-
creases in the frequency of the radiation by multiples of this
value. Specifically, 274 nm is 1064/3 plus 234155, 266 nm
is 1064/4, 253 nm is 1064/2 plus 534155, 246 nm is 1064/3
plus 334155, and 240 nm is 266 plus 4155. The spectra
shown are for the gas phase. Spectra of pyrazine were also
obtained in acetonitrile and methanol solutions. The signifi-
cant but small differences between the spectra obtained in
solution and in the gas phase will be discussed in another
publication.
V. RESULTS AND DISCUSSION
Although the present experimental RR spectra corre-
spond to excitation of the S 2 state, we briefly discuss the
spectroscopy of the S 1 state from the theoretical point of
view. This is particularly of interest in order to exhibit the
qualitative differences of the effects of the vibronic coupling
on the S 1 and S 2 RR spectra, respectively. Unlike the diffuse
absorption band of the S 2 state ~see below!, the S 1 absorption
spectrum of pyrazine exhibits well resolved peaks ~mostly
due to vibrational activity in the modes n6a , n9a , n10a !, which
give rise to strong single-level fluorescence emission. Single-
level fluorescence spectra have been calculated for the
FIG. 1. ~a! Experimental ~Ref. 20! and ~b! calculated preresonance Raman
spectra of the S 1 (n p * ) state of pyrazine obtained for the excitation wave-
length l5337 nm.
present model47 and are in good agreement with
experiment.5,6 Since we wish to focus here on RR emission,
these spectra will not be considered.
As a representative example of S 1 Raman emission, Fig.
1 presents a preresonant Raman spectrum of pyrazine ob-
tained with excitation at 337 nm. Panel ~a! shows the experi-
mental data of Suzuka et al.,20 panel ~b! shows the theoreti-
cal spectrum obtained with the present seven-mode ab initio
model. For better comparison with experimental data, the
computed intensities are plotted at the energetical position
determined by the measured ground state frequency of the
corresponding vibrational quantum. To simulate the experi-
mental resolution, the Raman lines of all reported spectra
have been convoluted with a Lorentzian of 10 cm21 FWHM.
The S 1 RR spectrum is dominated by the strong excita-
tion of the fundamental of n10a , which derives its intensity
through vibronic coupling from the S 2~pp*! state. The cal-
culation reproduces nicely the strong excitation of n10a as
well a the relative intensities of the excitations in the n1 , n6a ,
n8a , n9a vibrational modes, except that the fundamental of n1
is somewhat exaggerated. The peak at 1500 cm21 represents
~to about equal parts! the excitation of 10a16a and 234.
Furthermore the calculation predicts significant intensity of
2314, which lies outside the frequency range covered by the
experiment. Finally, it is noteworthy that all seven vibra-
tional modes incorporated in the ab initio model do show up
in the spectrum.
Figure 2~a! shows the room temperature gas-phase ab-
sorption profile of the S 2 band of pyrazine.38 By analogy
with the S 2 state of benzene,48 it can be assumed that the

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Stock et al.: Raman spectroscopy of pyrazine 6857

FIG. 3. Experimental ~a! and calculated ~b! resonance Raman spectra of the
S 2~pp*! state of pyrazine obtained for the excitation wavelength l5274
nm.

whereas the envelopes of the two calculations are rather

FIG. 2. ~a! Experimental ~Ref. 38! and ~b! calculated absorption of the
S 2~pp*! state of pyrazine. The stick spectrum in ~b! represents the vibronic
energy levels and absorption intensities of the seven-mode model; the enve-
lope is obtained by including a phenomenological electronic dephasing
~T 2535 fs!.
similar.
The remainder of this section is devoted to the discus-
sion of S 2 RR spectra of pyrazine, in particular to the com-
parison of theoretical and experimental data. Figures 37
show the experimental @panels ~a!# and theoretical @panels
~b!# S 2 RR spectra of pyrazine obtained for excitations at
273.9, 252.6, 245.9, and 239.5, nm, respectively. For consis-
tency, all spectra are plotted up to a Stokes shift of 3000
cm21, although for excitation near the center of the S 2 ab-
sorption band ~i.e., for l5253 nm and l5246 nm! further
overtones and combinations of the modes n1 and n6a appear
with measurable intensities at Stokes shifts beyond 3000
cm21. As in Fig. 1, experimental values of the vibrational
frequencies of pyrazine in the electronic ground state have
been used to determine the line positions of the theoretical
spectra.

spectrum would not change under supersonic-jet conditions,

i.e., it is truly homogeneously broadened. Figure 2~b! shows
the calculated absorption spectrum, which reproduces the ex-
periment in Fig. 2~a! in almost every detail. The envelope in
Fig. 2~a! has been obtained by including a phenomenological
electronic dephasing ~T 2535 fs!. The stick spectrum repre-
sents the vibronic energy levels and absorption intensities of
the seven-mode model Hamiltonian ~5!, and has been ob-
tained with the Lanczos algorithm.45,46 The very high density
of vibronic levels reflects the dissolution of the S 2 Born
Oppenheimer levels into the dense manifold of levels of the
lower-lying S 1 surface. It is clear that the irregularly spaced
and diffuse structures of the absorption profile are not assign-
able in term of harmonic vibrational modes in the S 2 state. A
comparison with previous four-mode calculations23,27 reveals
that the stick spectrum shows significant differences as a
consequence of the inclusion of three additional modes, FIG. 4. Same as Fig. 3 except l5266 nm.

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6858 Stock et al.: Raman spectroscopy of pyrazine
FIG. 5. Same as Fig. 3 except l5253 nm.
For all excitation wavelengths, the fundamentals, over-
tones and combination levels of n1 and n6a dominate the
observed spectra. The fundamental of n1 at '1000 cm21
corresponds to the strongest peak in all spectra. Excitation at
274 nm, near the red edge of thee S 2 absorption band, yields
mainly excitation of the n1 and n6a fundamentals, whereas
overtones and combination levels are weak @Fig. 3~a!#. Exci-
tation near the center of the S 2 absorption band ~266 and 253
nm! leads to significantly enhanced intensity of n1 and n6a
overtones and combination levels @Figs. 4~a!, 5~a!#. This en-
hancement of higher levels gradually disappears when the
excitation frequency approaches the blue edge of the S 2 ab-
sorption band @Fig. 7~a!#.
The theoretical RR spectra @panel ~b!# are seen to repro-
duce the enhancement of overtone intensity for excitation
near the center of the S 2 absorption band. The relative inten-
sities of the peaks corresponding to 1, 6a, 116a, 231, 231
16a, etc., are generally accurately reproduced. The modes
9a, 8a, 4 and 14, which are included in the calculation, lead
FIG. 6. Same as Fig. 3 except l5246 nm.
J. Chem. Phys., Vol. 103, No. 16, 22 October 1995
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FIG. 7. Same as Fig. 3 except l5239 nm.
to weak but discernible peaks in the spectra. To exemplify
that also weaker excitations are reproduced with high accu-
racy, consider the neighboring peaks 236a and 9a. In nice
agreement of experiment and theory the relative intensity
ratio R of the two peaks changes from R,1 ~Fig. 3! to R.1
~Figs. 4 and 5! to R'1 ~Fig. 6! to R,1 ~Fig. 7!. These
details indicate that the dynamics in the S 2 state of pyrazine,
as far as it is reflected in the RR spectrum, is rather accu-
rately described by the present ab initio vibronic-coupling
model.
It is particularly interesting to note that the nontotally
symmetric coupling mode n10a , which dominates the S 1 RR
spectrum ~Fig. 1!, is hardly observed under resonant excita-
tion of the S 2 state of pyrazine. In agreement with experi-
ment, the calculation predicts that the peaks 10a, 2310a
and 6a110a appear with very low intensity for excitation
wavelengths shorter than 274 nm. Considering the crucial
role of the mode n10a for the S 2 S 1 internal-conversion
process as the promoting mode as well as an important ac-
cepting mode,21 the inactivity of this mode in the S 2 RR
spectrum is remarkable. This observation underlines that the
RR spectrum carries only limited information on the photo-
physical dynamics in the excited states.
The agreement between experiment and calculation de-
teriorates for shorter excitation wavelengths. This is particu-
larly conspicuous for excitation at 239 nm ~Fig. 7!. In this
case the current level structure is reproduced by the calcula-
tion, but the calculated intensity of overtones and combina-
tion levels is too high relative to the intensity of the funda-
mentals. It is to be expected that for excitation at the blue
side of the S 2 absorption band of pyrazine higher excited
electronic states have to be considered in the calculation,49
i.e., the electronic three-state model ~5! may break down.
Specifically, one expects off-resonance contributions to the
fundamental transitions from higher-lying states. This pre-
sumes that n6a and n1 are achieved in some nearby higher
state~s!, which could be tested with experiments at shorter
wavelengths. The more immediate concern that such activity
makes a significant contribution to the spectrum obtained at
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Stock et al.: Raman spectroscopy of pyrazine 6859

FIG. 8. Calculated resonance Raman spectrum of the S 2~pp*! state of pyrazine as obtained by the ab initio three-state seven-mode model. The S 2 Raman
emission is plotted as a function of both excitation wavelength and Raman shift. We have added the absorption spectrum ~arbitrary scale! and indicated the
excitation wavelengths used in the experiment.

239 nm requires a relative intensity determination so that
spectra obtained at different wavelengths can be put on the
same relative intensity scale. Overall, however, one can con-
clude that the present three-state seven-mode model is well
justified and provides a rather comprehensive description of
the Raman spectra in resonance with the S 1 and S 2 states of
pyrazine.
Figure 8, finally, presents a survey of the calculated S 2
RR spectra, showing the Raman emission as a function of
both excitation wavelength and Raman shift, that is, excita-
tion functions of the most prominent Raman lines. It is con-
spicuous that the shapes of the excitation functions of the 6a
and 1 fundamentals and of overtones and combination levels
are clearly different. The excitation functions of overtones of
nontotally symmetric modes such as 2314 are again differ-
ent, showing enhancement at considerably higher excitation
energies than the fundamentals of totally symmetric modes.
Figure 8 illustrates the wealth of information on excited-state
dynamics which can in principle be obtained by RR spectros-
copy.
VI. CONCLUSIONS
We have presented new experimental and theoretical
data on the RR spectroscopy of the S 1 and S 2 states of pyra-
zine. On the experimental side, we have obtained gas-phase
RR spectra at five excitation wavelengths within the S 2 ab-
sorption band. On the theoretical side, we have extended
recent CASSCF/MRCI calculations27 to obtain the complete
set of parameters of the Taylor expansion ~gradients as well
as Hessian matrices! of the S 1 and S 2 surface, at the S 0 equi-
librium geometry. Based on these ab initio data, we have
constructed a vibronic-coupling model which explicitly in-
cludes seven ~out of 24! vibrational modes. Employing a
time-dependent approach, we have calculated RR cross sec-
tions for this three-state seven-mode model, treating all in-
tramolecular couplings ~numerically! exactly. The calculated
spectra have been found to be in excellent agreement with
the experimental data. This demonstrates that the combina-
tion of modern ab initio electronic-structure theory and mul-
timode time-dependent wave packet propagation techniques
opens the possibility of first-principles predictions of RR
spectra for polyatomic molecules. The degree of agreement
between theory and experiment obtained in the present ap-
plication demonstrates the adequacy of the modeling of the
multidimensional diabatic PESs in terms of a Taylor expan-
sion with respect to normal-mode displacements as well as
the accuracy of the ab initio electronic-structure calculations.
It is encouraging that predictive calculations of RR spectra
are nowadays possible for molecules of this size, even when
complex non-BornOppenheimer dynamics associated with
surface crossings is involved.

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6860 Stock et al.: Raman spectroscopy of pyrazine

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