Theoretical study on the photoisomerization of azobenzene

Takeshi Ishikawa, Takeshi Noro, and Takayuki Shoda

Citation: J. Chem. Phys. 115, 7503 (2001); doi: 10.1063/1.1406975

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JOURNAL OF CHEMICAL PHYSICS VOLUME 115, NUMBER 16 22 OCTOBER 2001

Theoretical study on the photoisomerization of azobenzene

Takeshi Ishikawa and Takeshi Noro
Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
Takayuki Shoda
Yokohama Research Center, Mitsubishi Chemical Corporation, 1000, Kamoshida-cho, Aoba-ku,
Yokohama 227-8502, Japan
共Received 19 June 2001; accepted 9 August 2001兲
Ab initio calculations are performed to elucidate the mechanism of the photoisomerization of
azobenzene. We obtain the excitation energies of the S 1 (n→ ␲ * ), S 2 ( ␲ → ␲ * ), and S 3 (n 2
→ ␲ * 2 ) states by complete active space self-consistent field 共CASSCF兲 and multireference single
double configuration interaction 共MRSDCI兲 calculations. Two-dimensional potential surfaces of the
ground- and excited states are obtained at the CASSCF level in order to investigate the
isomerization pathways. A conical intersection between the ground state and the S 1 state is found
near the midpoint of the rotation pathway, and causes a radiationless transition. On the other hand,
the S 2 state has local minima at the cis and trans structures, so that the isomerization proceeds at the
S 2 surface following the deexcitation. © 2001 American Institute of Physics.
关DOI: 10.1063/1.1406975兴

I. INTRODUCTION should proceed along a steep and barrierless pathway. On the

Azobenzene undergoes cis–trans photochemical isomer-
ization following excitation to the S 1 (n→ ␲ * ) and the
S 2 ( ␲ → ␲ * ) states, providing the basis for various applica-
tions, such as light triggered switches and image storage
devices.1–3 These processes have been extensively investi-
gated by various experimental methods, such as UV-visible
absorption,4 –7 Raman spectroscopy,8,9 and NMR.10
Bortolus and Monti11 investigated the quantum yields
for trans→cis( ␾ c ) and cis→trans( ␾ t ) photoisomerization
following excitations to the S 1 and to the S 2 bands in sol-
vents of different polarity. At both excitations, ␾ c increased
and ␾ t decreased with increasing polarity of the solvent. On
the other hand, the quantum yield of S 1 was twice as large as
that of S 2 in all of the solvents studied for both the
trans→cis and cis→trans processes. They suggested that this
wavelength dependence of the yield was not the result of
processes occurring in different excited states, but that only
one excited state, S 1 , was responsible for the photoisomer-
ization.
With respect to the photoisomerization itself, two differ-
ent pathways have been proposed: a twisting around the
NvN double bond 共rotation mechanism兲 and a planar varia-
tion of one of the C–N–N angles 共inversion mechanism兲.
The latter mechanism was supported by Rau and Lüddecke,
who observed a cis–trans photoisomerization reaction of two
azobenzenophanes for which inversion was the only possible
isomerization pathway.4
In recent studies, time-resolved measurements have been
performed and direct transient absorption data obtained.
Nägele et al.12 executed femtosecond transient absorption
measurements of the photoisomerization in the S 1 band. For
cis-azobenzene, they found an extremely fast photoproduct
formation with a dominating 170 fs and a weak 2 ps compo-
nent. The ultrafast isomerization indicated that the reaction
other hand, for trans-azobenzene, the reaction proceeds in
320 fs, much slower than the speed for cis-azobenzene.
These findings indicate that the reaction should proceed
along a gradual pathway. The potential curves of S 1 calcu-
lated by Monti et al.13 show a large barrier for the rotation
pathway, while the inversion pathway has no barrier and the
gradient of the slope on the cis-side is steep compared to that
on the trans-side. They therefore concluded that the isomer-
ization through S 1 is likely to proceed via an inversion path-
way.
Lednev et al.14,15 observed two transient absorptions
around 400 nm that had lifetime constants of 1 and 15 ps,
and one at 475 nm that had a lifetime shorter than 200 fs.
These transient absorptions were assigned to the bottleneck
states of the S 1 and S 2 potentials of Monti et al. They con-
cluded that the excitation of n→ ␲ * results in isomerization
along the inversion pathway, whereas that of ␲→␲* results
in isomerization along the rotation pathway.
Fujino and Tahara16 conducted a time-resolved reso-
nance Raman study of trans-azobenzene in solution and
obtained structural information of the transients. They pre-
sented Raman spectra of the 400-nm transient assigned to
S 1 . The NvN stretch frequency in the transient was very
close to that of the ground state 共1428 cm⫺1 in S 1 and
1440 cm⫺1 in the ground state兲. They concluded that the
double bond nature of the NvN bond is retained throughout
the photoisomerization, which allows the inversion pathway
to proceed.
On the other hand, there have been only a few theoreti-
cal studies investigating the photoisomerization of azoben-
zene. Monti et al.13 performed small configuration interac-
tion 共CI兲 calculations using the STO-3G basis set for the
ground- and excited states at four geometries, i.e., the trans-
and cis isomers and activated complexes along the rotational
and the inversion pathways. The obtained potential curves

0021-9606/2001/115(16)/7503/10/$18.00 7503 © 2001 American Institute of Physics

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7504 J. Chem. Phys., Vol. 115, No. 16, 22 October 2001 Ishikawa, Noro, and Shoda

TABLE I. Optimized geometries of azobenzene. Distances in Å, angles in TABLE III. Bond orders of NN bond and NC bond.
degrees.
Bond order
Method Structure ⬔CNNC ⬔NNCC ⬔NNC RNN RNC
Structure State NN NC
Ground state
CASSCF trans 0.0 0.0 115.0 1.24 1.42 trans Ground state 1.49 0.94
CASSCFa 0.0 0.0 114.2 1.259 1.438 S 1 (n→ ␲ * ) 1.07 0.96
X rayb 0.0 0.0 114.1 1.247 1.428 S 2( ␲ → ␲ *) 0.95 1.05
CASSCF cis 180.0 56.0 123.0 1.24 1.43 S 3 (n 2 → ␲ * 2 ) 1.23 1.00
CASSCFa 180.0 60.8 121.9 1.240 1.472 cis Ground state 1.55 0.92
X rayc 180.0 53.3 121.9 1.253 1.449 S 1 (n→ ␲ * ) 1.09 0.90
S 1 (n→ ␲ * ) S 2( ␲ → ␲ *) 1.00 0.95
CASSCF rotamer 45.0 ⫺3.0 126.0 1.26 1.38 S 3 (n 2 → ␲ * 2 ) 0.82 0.94
CASSCFa 55.0 5.6 126.3 1.251 1.394
S 2( ␲ → ␲ *)
CASSCF trans 0.0 0.0 110.0 1.33 1.35
cis 180.0 35.0 126.0 1.23 1.32 S 1 (n→ ␲ * ), S 2 ( ␲ → ␲ * ), and S 3 (n 2 → ␲ * 2 ) states using a
S 3 (n 2 → ␲ * 2 ) moderate size basis set. The third singlet state having the
CASSCF rotamer 90.0 ⫺6.0 126.0 1.26 1.38 n 2 → ␲ * 2 configuration will be referred to as S 3 instead of
a S 2 , because S 2 is commonly used for the ␲→␲* state. The
Reference 17.
b
Reference 22. excitation energies and global potential curves are calculated
c
Reference 23. to give reliable information for the isomerization of azoben-
zene.
In the next section, we will explain the calculational
have provided a rough image of the isomerization pathways method. The results of the calculations are given in Sec. III.
that has been adopted in many experiments and is often used The pathways of photoisomerization are discussed in Sec. IV,
for the assignment of the transient absorptions. However, followed by conclusions.
because of the quality of the basis set, the size of the CI, and
the accuracy of the calculated excitation energies, it is diffi- II. METHOD OF CALCULATIONS
cult to conclude that their potential curves are absolutely A. Basis set
reliable. Recently, Cattaneo and Persico17 performed
CASSCF and multireference perturbation calculations to ob- We employed two types of basis sets. In the smaller set,
tain the optimized geometries, excitation energies, and po- we used a double zeta with contraction 共421/31兲 for nitrogen,
tential curves for the ground state and the low-lying singlet- and a minimal zeta with contraction 共43/4兲 for carbon, both
and triplet excited states. Although the resulting potential of which were prepared by Tatewaki and Huzinaga.18 For
curves of the S 1 and S 2 states appeared to be different from hydrogen, Duijneveldt’s (5s) 19 was employed. In the larger
those of Monti et al., Catteneo and Persico supported the set, we added a polarization function of d(0.864) for nitro-
current view that inversion is the preferred pathway for the gen, and decontracted valence part of 共43/4兲 to 共421/31兲 for
ground-state isomerization, and that such inversion probably carbon.
occurs via n→ ␲ * excitation, while rotation occurs by
B. Geometry optimization
␲→␲* excitation.
In this work, we carry out complete active space self- Azobenzene has C 2h and C 2 symmetries in the trans-
consistent field 共CASSCF兲—multireference single and and cis structures, respectively. We performed geometry op-
double excitation 共MRSD兲 CI calculations for the ground, timizations for the ground, S 1 , S 2 , and S 3 states, at trans-

TABLE II. Excitation energies 共eV兲 of trans- and cis-azobenzene.

Vertical Adiabatic

trans CASSCFa CASSCFb MRSDCI CIPSIc MRSDCI Expt.d

S 1 (n→ ␲ * ) 2.85 3.48 3.11 2.81 2.88 2.79

S 2( ␲ → ␲ *) 7.62 6.26 5.39 4.55 5.01 3.95
S 3 (n 2 → ␲ * 2 ) 6.02 6.37 6.56 4.61
Vertical Adiabatic

cis MCSCFa MCSCFb MRSDCI CIPSIc MRSDCI CIPSIc Expt.d

S 1 (n→ ␲ * ) 3.65 4.53 3.95 2.94 3.54 2.75 2.82

S 2( ␲ → ␲ *) 8.62 6.80 6.12 4.82 6.47 5.09 4.77
S 3 (n 2 → ␲ * 2 ) 5.32 6.37 5.56 4.80 4.67
a
CASSCF with the smaller basis set.
b
CASSCF with the larger basis set.
c
Reference 17.
d
Reference 24.

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J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 1. Potential surface and contour map of the ground state of azobenzene. The ⬔NCC was fixed at 115°, while the other five parameters were optimized
for each ⬔NCCN and ⬔NNCC.
and cis structures by CASSCF where five orbitals including
two nonbonding MOs 共n 1 and n 2 兲, ␲ and ␲* span an active
space using the smaller basis set. The C 2 symmetry was
maintained for both the trans- and cis isomers. The C–C and
C–H distances and angles of two phenyl groups were main-
tained at 1.394 Å, 1.090 Å, and 120°, respectively, through-
out the variation of parameters.
C. Excitation energies
For the equilibrium geometries, we carried out MRSDCI
calculations to obtain excitation energies of the S 1 , S 2 , and
S 3 states using two basis sets. We picked up important con-
figuration state functions 共CSFs兲 from the MCSCF wave
function of each state and employed them as reference func-
tions in the calculation of CI, in which single and double
excitations from the occupied MOs were considered. The
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Isomerization of azobenzene 7505
MOs arising from 1s and 2s of nitrogen and carbon were
kept frozen in generating CSFs. The dimension of CI ranged
from 5 000 000 to 9 000 000.
D. Potential surface
In order to investigate the isomerization pathways of ro-
tation and inversion, we calculated the potential surfaces of
the ground and excited states by CASSCF using the smaller
basis set. We took the dihedral angle ⬔CNNC and one of the
bending angles ⬔NNC as axes of the two-dimensional sur-
face. At each ⬔CNNC and ⬔NNC, we optimized the re-
sidual parameters with the exception of another bending
angle ⬔NNC and two phenyl groups, which were fixed at
115° and the experimental values of the ground state, respec-
tively.
The same active space as for the geometry optimization
was used and four state-average CASSCF calculations were
7506 J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 2. Potential surface and contour map of the S 1 (n→ ␲ * ) state of azobenzene. The ⬔NCC was fixed at 115°, while the other five parameters were
optimized for each ⬔NCCN and ⬔NNCC.
performed. All the calculations were carried out using the
software package ALCHEMY II20 and GAMESS.21
III. RESULTS
A. Optimized geometries
Table I summarizes the optimized geometries of the
ground states and excited states along with the previous the-
oretical and experimental data. For the ground state of trans-
and cis-azobenzene, the geometry parameters calculated by
CASSCF were in good agreement with those derived experi-
mentally, to within an error of 3° and 0.01–0.09 a.u. for the
bond angles and the bond distances, respectively. The present
results showed a similar tendency to that by the CASSCF
calculations by Cattaneo and Persico.17
For the excited states, no geometrical parameter was
available from the experiments. However, we might expect
that qualities of the calculated parameters will be similar to
those of the ground state. For S 1 , we found a shallow mini-
mum in the rotational pathway that was very close to the
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Ishikawa, Noro, and Shoda
transition point obtained by Cattaneo and Persico. The R NN
of 1.26 Å differed from that of the ground state of the trans
structure by only 0.02 Å. The S 2 state had minima in both
the trans and cis structures. The S 3 (n 2 → ␲ * 2 ) state also had
a deep minimum at the midpoint of the rotational pathway,
which was very close to the minimum point of the S 1 state.
B. Excitation energies
The calculated vertical excitation energies are summa-
rized in Table II. We also list the previous theoretical results
and the available experimental results for comparison.
At the CASSCF level, the calculated excitation energies
are all higher than the corresponding experimental values.
For S 1 in the trans form, we obtained fairly good agreement
with the experimental values. The smaller set yielded 2.85
eV compared with the experimental value of 2.79 eV. The
enlargement of the basis set increased the error by 0.6 eV, but
the inclusion of electron correlation decreased the error by
0.3 eV. When we calculated the adiabatic excitation energy
J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 3. Potential surface and contour map of the S 2 ( ␲ → ␲ * ) state of azobenzene. The ⬔NCC was fixed at 115°, while the other five parameters were
optimized for each ⬔NCCN and ⬔NNCC.
by optimizing the geometrical parameters—except R NN and
the dihedral angle—we obtained an excitation energy of 2.88
eV. In the cis structure, the discrepancy of the calculated
value increased by 0.5–1.0 eV.
For the S 2 state in the trans form, the CASSCF calcula-
tion gave 7.62 eV with the smaller set, while the larger set
yielded the better value of 6.26 eV. The inclusion of electron
correlation reduced the error by 1 eV, and the optimization of
geometry led to a further improvement of 0.4 eV. However,
we still have a discrepancy of 1.0 eV compared with the
experimental value. The S 2 state in the cis form showed ten-
dencies similar to those for the trans form. The contribution
of electron correlations was again considerably large.
For the S 3 (n 2 → ␲ * 2 ) state, the calculated and experi-
mental results could not be compared. Comparing the present
results with the recent results of CIPSI by Cattaneo and Per-
sico, we find that the present excitation energy is approxi-
mately 1.7 eV higher at the CI level for both the trans- and
cis-structures. Because we considered only the electron cor-
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Isomerization of azobenzene 7507
relations among valence electrons, the effects of core elec-
trons might be considerably large.
We calculated two-dimensional potential surfaces by the
CASSCF using the small set, which gave reasonable excita-
tion energies for S 1 but yielded S 3 and S 2 energies that were
2– 4 eV too high.
C. Bond order
Table III lists the bond orders of the NvN and N–C
bonds of the ground- and excited states at the optimized
geometry of the ground state in the cis- and trans-forms. The
recent time-resolved measurements provide structural infor-
mation on the transients. The bond orders should provide
valuable information to those experimentalists. The bond or-
der of the NvN bond is approximately 1.5 for the ground
state, considerably smaller than the formal value of the
double bond of 2.0. For S 1 and S 2 , the bond order decreased
by approximately 0.5 due to the excitation from a bonding
7508 J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 4. Potential surface and contour map of the S 3 (n 2 → ␲ * 2 ) state of azobenzene. The ⬔NCC was fixed at 115°, while the other five parameters were
optimized for each ⬔NCCN and ⬔NNCC.
orbital to antibonding orbitals. Thus, these excited states
lose the double bond nature of the NvN bond. The S 3 (n 2
→ ␲ * 2 ) state shows a different behavior. At the trans struc-
ture, the bond order is 1.23, which is considerably larger
than those of other excited states, while it decreases by 0.41
at the cis structure.
Fujino and Tahara16 observed that the NvN stretch
frequency in the transient in the S 1 state is very close to that
of the ground state and concluded that the double bond
nature of the NvN bond is retained throughout the photo-
isomerization, thereby allowing the inversion pathway to
proceed. However, the S 1 state loses the double bond na-
ture at the trans- and cis structures, judging from the bond
order.
D. Potential surfaces
In Figs. 1– 4, we plotted the potential surfaces and con-
tour maps for the ground, S 1 , S 2 , and S 3 states.
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Ishikawa, Noro, and Shoda
As can be clearly seen, the ground- and the S 3 states
make a pseudocrossing along the rotation pathway. When
azobenzene goes from the trans to the cis form via the rota-
tion pathway, the n 1 , n 2 , ␲, and ␲* orbitals change to the ␲,
␲*, n 1 , and n 2 orbitals, respectively, as shown in Fig. 5. The
ground state has the n 21 n 22 ␲ 2 configuration in both the trans
and cis forms. To keep this configuration, the interchange of
the n 2 and ␲* must be compensated by the exchange of the
configurations between n 21 n 22 ␲ 2 and n 21 ␲ 2 ␲ * 2 , which causes
a large barrier and deep minimum due to the pseudocrossing
in the potential surfaces.
On the other hand, the interchange of the orbitals n 1
and ␲* means only the exchange of open-shell orbitals in the
S 1 state. Thus, we obtained a barrierless potential for S 1 .
The potential curves by Cattaneo and Persico also seem to be
flat. The situation is completely different from that in the
results of Monti et al., which have provided a theoretical
basis for many experiments. Their curve has a large barrier
and a pseudocrossing with S 2 , which causes bottlenecks.
J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 5. Contour maps of important MOs on the rotation pathway.
Many experiments assigned the transient states to these
bottlenecks.
In the rotation pathway, we see a flat valley on the trans-
side, a shallow minimum near the midpoint, and a steep
slope on the cis-side. This minimum point is very close to
the ridge of the ground state, and the ground- and S 1 states
come into close proximity there. In Fig. 6, we show the
precise surfaces of the ground- and S 1 states at this area. In
FIG. 6. Potential surfaces of the ground and S 1 (n→ ␲ * ) states around the
mid-point of the rotation pathway.
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Isomerization of azobenzene 7509
the calculation of the precise surfaces, we also optimized
another bending angle ⬔NNC which was fixed in the calcu-
lation of the global potential surfaces. This figure strongly
suggests the existence of a conical inter-
section of these states. At the angles ⬔CNNC⫽88° and
⬔NNC⫽130°, the energy separation of these states was
only 0.07 eV. We did not find a conical intersection precisely
locating in the C 2 symmetry. We also show the bond order of
the NvN bond of these states in two-dimensional surface for
the ground- and S 1 state in Figs. 7 and 8, respectively. In the
crossing area, the bond order of these states changes rapidly,
i.e., the ground state loses its double bond nature and the S 1
gains a double bond nature. This interchange of the character
of the wave functions also suggests that the conical intersec-
tion is located near this area. Furthermore, the sharp maxi-
mum in the bond order of S 1 at the angles ⬔CNNC⫽88°
and ⬔NNC⫽130° was not due to the interaction with the
ground state but rather to interaction with the S 3 state. This
suggests that the S 3 state also interacts with these states in
this area. On the other hand, we did not find such a drastic
change of the wave function in the inversion pathway or
other areas.
In the potential surface of S 2 , we found shallow double
minima along the rotation pathway, and a large barrier along
the inversion pathway. As mentioned in the previous section,
the present CASSCF calculation provided a poor description
of this state. When we subtract the error of 4 eV from the
potential curve, we have a conical intersection with S 3 , as
found by Cattaneo and Persico.
7510 J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 7. Bond order of the NN bond in the ground state.
IV. DISCUSSION
In this section, we attempt to clarify the mechanism of
the photoisomerization of azobenzene based on the calcu-
lated potential surfaces.
A. Isomerization after the excitation to S 1
First, let us discuss the isomerization after the excitation
to S 1 . We mentioned that a conical intersection between the
ground- and S 1 states exists near the shallow minimum point
in the rotational pathway. We do not find any other points at
which the wave function changes rapidly. Thus, we may con-
clude that the transition occurs in the vicinity of this conical
intersection. When the trans-isomer absorbs a photon, the
system gradually changes its geometry in the direction of this
transition point. On the other hand, when we start from the
cis form, the system reaches the minimum point quickly us-
ing the steep slope. This is the reason why the isomerization
proceeds faster for the cis-isomer than for the trans-isomer.
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Ishikawa, Noro, and Shoda
B. Isomerization after the excitation to S 2
In the potential surface of the S 2 state, there are local
minima in both the trans- and cis-isomers. Thus, the iso-
merization does not occur on this potential surface. As
Cattaneo and Persico suggested, the S 2 state deexcites to
S 3 (n 2 → ␲ * 2 ) nonadiabatically through the conical inter-
section. The S 3 state has strong interactions with the ground-
and S 1 states. Thus, the isomerization should proceed after
deexcitation to the S 1 or S 3 states. This isomerization
mechanism partly supports the speculation of the experi-
ments that the processes from the S 2 state do not occur in
the S 2 surface, but the S 1 state is responsible for this photo-
isomerization.
C. Rotation versus inversion pathways
As mentioned in the Introduction, the rotation and inver-
sion pathways have been proposed as two possible mecha-
J. Chem. Phys., Vol. 115, No. 16, 22 October 2001
FIG. 8. Bond order of the NN bond in the S 1 (n→ ␲ * ) state.
nisms responsible for the photoisomerization of azobenzene.
Recent experimental studies seem to support the inversion
pathway in the photoisomerization after the S 1 transition.
However, many studies, such as Nägele et al. and Lednov
et al., have explained their results using the potential curves
of Monti et al., which have a high barrier along the rotational
pathway and unreasonable bottle necks for S 1 .
The potential curves of Cattaneo and Persico include
electron correlation effects and are much more reliable than
those of Monti et al. The feature of their potential curves are
in fair agreement with the surfaces in the present study.
However, Cattaneo and Persico concluded that the inversion
is probably the favored pathway for the photoisomerization.
However, they could not rule out the participation of the
rotation based solely on the shape of their potential curves.
They expected that certain modifications of the potential
curves due to solvent effects may have influenced the reac-
tion mechanism.
Fujino and Tahara also supported the inversion pathway
by not using the potential curve by Monti et al., but their
results on the stretching frequencies of the transients. They
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Isomerization of azobenzene 7511
reported the NvN stretch frequency in a transient was
very close to that of the ground state 共1428 cm⫺1 in S 1 and
1440 cm⫺1 in the ground state兲. The double bond nature of
the NvN bond was retained throughout the photoisomeriza-
tion, allowing the inversion pathway to proceed. However,
the bond order of the NvN bond of the S 1 is approximately
1.0, which is far from that of the double bond nature. The
bond order of the NvN bond increased in the vicinity of the
conical intersection points along the rotation pathway, result-
ing in the double bond nature. In this work, although we did
not perform vibrational analysis, only population analysis, it
is difficult to accept, based on the results, that the double
bond nature is retained along the inversion pathway.
Lednev et al. observed a transient band with a decay
life time of 2.5⫾0.2 ps on excitation at 503 nm, close to the
S 1 origin and an additional fast component of 0.6 ps on
excitation at 390 or 420 nm, both well above the threshold.
The slow component seems to correspond to the isomeriza-
tion process along the rotation pathway, while we cannot
find a decay path corresponding to the additional fast com-
ponent.
7512 J. Chem. Phys., Vol. 115, No. 16, 22 October 2001 Ishikawa, Noro, and Shoda

V. CONCLUSIONS 1
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共1990兲.
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for the trans- and cis- azobenzenes. The calculated geom- 485 共1992兲.
etries of the ground state were in good agreement with those
3
T. Ikeda and O. Tsutsumi, Science 268, 1873 共1995兲.
4
H. Rau and E. Lüddecke, J. Am. Chem. Soc. 104, 1616 共1982兲.
obtained experimentally. The excitation energies of the 5
H. Rau, J. Photochem. 26, 221 共1984兲.
S 1 (n→ ␲ * ) and S 3 (n 2 → ␲ * 2 ) states were in reasonably 6
H. Rau and S. Yu-Quan, J. Photochem. Photobiol., A 42, 321 共1988兲.
7
good accord with the experimental results for the two iso- N. Siampringue, G. Guyot, S. Monti, and P. Bortollus, J. Photochem. 37,
mers at the MCSCF and CI levels. On the other hand, the 185 共1987兲.
8
H. Okamoto, H. Hamaguchi, and M. Tasumi, Chem. Phys. Lett. 130, 185
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N. Biswas and S. Umapathy, Chem. Phys. Lett. 236, 24 共1995兲.
Two-dimensional potential surfaces were calculated for 10
R. D. Curtis, J. W. Hilborn, G. Wu, M. D. Lumsden, R. E. Wasylishen, and
these four states at the MCSCF level to investigate the J. A. Pincock, J. Phys. Chem. 97, 1856 共1993兲.
11
P. Bortolus and S. Monti, Phys. Chem. 83, 648 共1979兲.
trans–cis isomerization processes. The obtained surfaces 12
T. Nägele, R. Hoche, W. Zinth, and J. Wachteitl, Chem. Phys. Lett. 272,
were considerably different from those of Monti et al., 48 共1997兲.
which have been widely used to explain experimental 13
S. Monti, G. Orlandi, and P. Palmieri, Chem. Phys. 71, 87 共1982兲.
14
results. I. K. Lednev, T.-Q. Ye, R. E. Hester, and J. N. Moore, J. Phys. Chem. 100,
13333 共1996兲.
In the calculated potential surface, we found a conical 15
I. K. Lednev, T.-Q. Ye, P. Matousek, M. Towrie, P. Foggi, F. V. R. Neu-
intersection between the ground- and S 1 states near the mid- wahl, S. Umapath, R. E. Hester, and J. N. Moore, Chem. Phys. Lett. 290,
way of the rotational pathway. We did not find any other 68 共1998兲.
points at which the wave function changed rapidly. Thus, it is
16
T. Fujino and T. Tahara, J. Phys. Chem. A 104, 4203 共2000兲.
17
P. Cattaneo and M. Persico, Phys. Chem. Chem. Phys. 1, 4793 共1999兲.
plausible that the transition occurs in the vicinity of this 18
S. Huzinaga, J. Andzelm, M. Klobukouwski, E. Radzio-Andzelm, Y. Sa-
conical intersection. In the S 2 state, local minima exist in kai, and H. Tatewaki, Gaussian Basis Sets for Molecular Calculations
both the trans- and cis-structures, so that the isomerization 共Elsevier, New York, 1984兲.
may not occur on the surface. After deexcitation to S 3 or S 1 ,
19
Van Duijneveldt, IBM Research Report RJ945 共1971兲.
20
B. H. Lengthfield III, J. Chem. Phys. 73, 382 共1980兲; B. Liu and M.
the isomerization takes place.
Yoshimine, ibid. 74, 612 共1981兲; B. H. Lengthfield III, and B. Liu, ibid.
75, 478 共1981兲.
21
ACKNOWLEDGMENTS M. W. Schmidt, K. K. Baldridge, J. S. Goatz et al., J. Comput. Chem. 14,
1347 共1993兲.
22
The authors would like to thank Professor K. Tanaka, Dr. J. A. Bouwstra, A. Schouten, and J. Kroon, Acta Crystallogr. C39, 1121
共1983兲.
M. Sekiya, and Dr. K. Nobusada for their helpful suggestions 23
A. Mostad and C. Romming, Acta Chem. Scand. 25, 3561 共1971兲.
and discussion. The authors would also like to thank Dr. M. 24
H. Ran, in Photochromism: Molecular and Systems, edited by H. Durr and
Yoshimine for providing the ALCHEMY II software package. H. Bouas-Lauran 共Elsevier, Amsterdam, 1990兲, p. 165.

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