Electronic Spectrum and Structure of

Azulene
Cite as: J. Chem. Phys. 25, 1112 (1956); https://doi.org/10.1063/1.1743159
Submitted: 12 January 1956 • Published Online: 06 October 2004

Rudolph Pariser

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THE JOURNAL OF CHEMICAL PHYSICS VOLUME 25. NUMBER 6 DECEMBER. 1956

Electronic Spectrum and Structure of Azulene*

RUDOLPH PARISER
Jackson Laboratory, E. I. du Pont de Nemours and Co., Wilmington, Delaware
(Received January 12, 1956)

A previously given theoretical method is applied to the azulene molecule ....-electron energies, transtion
moments, dipole moments, charge distributions, and bond orders are calculated for the ground state and for
the lower singlet and triplet excited states.
The same detailed procedure which had previously given good results for the polyacenes is used here.
Configuration interaction is included for all singly excited configurations. Two parallel calculations, one
starting with conventional Huckel MOs and the other with perimeter MOs, are carried through.
Huckel MOs lead to numerical results in good agreement with available experimental spectral data. In
this connection some previous assignments are confirmed and some new ones are proposed. For the ...-electron
dipole moment for the ground state, one calculates 1.88 D with Huckel MOs and 3.36 D with perimeter
MOs; the experimental value is 1 D.
One may conclude that the present procedure gives results in substantial agreement with experiment
provided that good MOs, e.g., Huckel MOs, are employed. For computation of excited state energies it is
essential to include interaction among nearly degenerate configurations. More extensive configuration
interaction, however, appears to improve the transition energies and especially the transition moments
and dipole moments.

I. INTRODUCTION has not been very satisfactory. Moffitt 6 has recently

A ZULENE has received considerable attention
from both a theoretical and experimental point
of view. Although azulene is an isomer of naphthalene
and like naphthalene has a bicyclic unsaturated struc-
ture, it differs greatly in its properties from aromatic
molecules built up from six membered rings. In fact it
is the geometry of this molecule, consisting, so to speak,
of the fusion of a five and seven membered ring, which
is chiefly responsible for its blue color and large dipole
moment. It is the purpose of this note to add to the
understanding of the spectral and other electronic
properties of azulene through an attempt to calculate
these by theoretical methods.
Early theoretical treatments l - 5 have achieved notable
success in pointing out the basic causes for the dipole
moment in azulene and for the bathochromic displace-
ment of its spectrum relative to that of naphthalene,
but quantitative agreement with experimental values
2 6
_-,/<0..-___
FIG. 1. The carbon skelton of azulene, the choice of axes, and the
defined positive direction of the dipole moment.
----
* Presented at the Molecular Quantum Mechanics Conference,
Austin, Texas, December 8, 1955.
1 A. L. Sklar, ]. Chern. Phys. 5, 669 (1937).
2 C. A. Coulson and H. C. Longuet-Higgins, Rev. Sci. lnstr. 15,
929 (1947).
• G. W. Wheland and D. E. Mann, J. Chern. Phys. 17, 264
(1949).
4 Mann, Platt, and Klevens, J. Chern. Phys. 18,481 (1949).
6 R. D. Brown, Trans. Faraday Soc. 44, 984 (1948).
applied a semiempirical theory designed for cata-
condensed hydrocarbons to the lower excited singlet
states in azulene, obtaining good results which are
particularily valuable in giving a clear insight into the
nature and origin of these states. Application of the
nonempirical SCF LCAO method 7 by Julg 8 •9 has been
rather successful for the dipole moment but not for the
energies of the lowest excited singlet and triplet; how-
ever, modification lo •12 of the one-center Coulomb in-
tegral improved these energies.
In the past few years a new theoretical method ll- 13
has found considerable application to various problems
in molecular spectra and structure. Very recently this
method has produced good results for the polyacenes,14
and its present application to azulene should serve as
a further test of its validity and utility.
II. METHOD AND PROCEDURE
The carbon skeleton structure of azulene is taken as
in Fig. 1, with the sides of the regular pentagon and
heptagon set equal to 1.390 A. The 1I"-electronic states
belong to the irreducible representations Al and BI of
the symmetry group C2V • Electronic transitions from
the ground state, IA I , to other lAI states will have the
transition moment directed along the long, or z axis,
+ whereas for transitions to IBI states it will be directed
along the short, or x axis.
The same detailed procedure which was used for
naphthalene is used here.t4 As for naphthalene, two
8 W. Moffitt, ]. Chern. Phys. 22, 320 (1954).
7 C. C. J. Roothaan, Revs. Modern Phys. 23, 69 (1951).
8 A. Julg, Compt. rend. 239, 1498 (1954).
9 A. Julg, ]. chim. phys. 52, 377 (1955).
10 R. Pariser, J. Chern. Phys. 21, 568 (1953).
11 R. Pariser and R. G. Parr, J. Chern. Phys. 21, 466 (1953).
12 R. Pariser and R. G. Parr, J. Chern. Phys. 21, 767 (1953).
13]. A. Pople, Trans. Faraday Soc. 49, 1375 (1953).
14 R. Pariser, J. Chern. Phys. 24, 250 (1956).

1112
 STRUCTURE OF AZULENE 1113

TABLE r. Azulene Huckel molecular orbitals.·

MO Sym (x,) (x,:l=x,) (X.:l=XIO) (x.:l=x.) (x,±x,) (x.) k

1 b2 0.27988 0.32330 0.46703 0.28864 0.19981 0.17297 2.31028
2 a2 0.00000 -0.22068 -0.29916 0.48406 0.35706 0.00000 1.35567
3 b2 -0.32427 -0.26777 -0.11798 0.19090 0.43327 0.52467 1.65157
4 b2 0.58294 0.25853 -0.35363 -0.21856 0.15978 0.36028 0.88698
5 a2 0.00000 0.54285 0.25908 0.16012 0.33550 0.00000 0.47726
6 a2 0.00000 -0.29916 0.22068 -0.35706 0.48406 0.00000 -0.73764
7 b2 0.31575 -0.06321 -0.29044 0.46994 0.10228 -0.51089 -0.40039
8 b2 -0.55268 0.43640 -0.13649 -0.08436 0.26971 -0.34157 1.57922
9 a2 0.00000 0.25908 -0.54285 -0.33550 0.16012 0.00000 -2.09529
10 b2 0.26749 -0.25000 0.19981 -0;32330 0.40450 -0.43280 -1.86921

• Note: By definition for the ith MO. </>, = ~ C.iX•. The C.;'s are listed under the corresponding x•. + and - refer to MOs of symmetry b, and a" respec-
tively. k's are eigenvalues of the resonance integral matrix, ~,which has the MOs as eigenvectors.

different sets of molecular orbitals are employed, the wave functions are also listed in Table II, and the
perimeter MOs6 and conventional semiempirical LCAO more important wave functions are presented in
MOs, i.e., HUckel MOs, which are listed in Table I. Table IIJ.l6
The perimeter MOs are numbered so as to correspond
to the HUckel MOs. The values for the one-center TABLE II. Calculated energies and oscillator strengths
Coulomb integral, nearest neighbor two-center Coulomb for azulene states.·
integral, and the core resonance integral, {3, are obtained
from the benezene spectrum.14 The other Coulomb HUckel MOs Perimeter M Os
integrals are calculated from Slater 2p AOs,1" with State Energy (ev) f Energy (ev) f
Z= 3.18, for the appropriate interatomic distances, and IA I : 1 0.000 Ref 0.000 Ref
penetration integrals are neglected (or assumed to 2 3.084 0.002 4.194 0.003
3 4.692 1.243 6.250 1.673
contribute equally to each C atom). 4 5.994 0.003 6.714 0.225
The maximum amount of configuration interaction 5 6.867 0.215 7.194 0.343
which is included here mixes the ground and all singly 6 7.018 0.199 7.717 0.003
7 7.385 0.350 8.075 0.111
excited configurations. This leads to a 14th-order secular
equation for the singlet I A I states, a 13th-ord.er equation IB,: 1 1.733 0.017 2.814 0.035
2 4.112 0.116 5.095 0.080
for the triplet 3A I states, and two 12th-order equations 3 5.604 0.365 5.872 0.422
for IBI and 3B I states, respectively. Since azulene is not 4 6.191 0.014 6.881 0.847
an alternant hydrocarbon, further factorization of the 5 7.018 0.278 7.709 0.003
l4 6 7.271 0.870 7.864 0.151
secular equation into plus and minus states is not
possible. The numerical calculation of the matrix 3A I : 1 1.840 0.000 2.426 0.000
2 2.440 0.006 3.211 0.001
elements for the secular equations, as well as the solu- 3 4.632 0.028 5.116 0.010
tion of these equations, were performed on a high- 4 4.752 0.082 5.329 0.095
speed digital computer, the International Business 5 5.725 0.018 6.178 0.019
6 5.929 0.000 6.846 0.010
Machines Corporation's ED PM 701, with use of the
same generalized program as for the polyacenes. 14 3B I : 1 1.468 Ref 2.232 Ref
Transition moments, dipole moments, bond orders, 2 3.496 0.008 4.249 0.028
3 4.076 0.068 4.540 0.073
and charge densities are calculated according to the 4 4.881 0.259 5.232 0.161
definitions which were given previously.14 5 5.439 0.000 6.023 0.007
6 6.533 0.100 7.210 0.045
III. RESULTS AND DISCUSSION Higher Energy States
Solution of the secular equations for interaction Huckel MOs: IA I : 7.551, 8.122,10.004,10.851,11.075, 11.561,
among all singly excited and the ground configurations 14.680; IB I : 8.129, 8.394, 9.185, 11.342, 11.716, 13.672; 3A I :
6.831, 7.401, 9.323, 10.373, 10.567, 11.355, 14.666; aB I : 7.186,
leads to a set of state energies and wave functions. 7.526, 8.887, 10.449, 11.661, 13.519.
Transition energies referred to the lowest energy state,
Perimeter MOs: IA I : 8.193, 8.616, 10.558, 11.207, 11.546,
or ground state, are listed in Table II. Referred to the 12.796, 13.517; IB,: 8.749, 9.137, 10.025, 10.503, 11.740, 13.040;
lowest energy configuration (that is, the configuration 3A I: 7.774, 8.156, 9.377, 10.181, 10.784, 12.722, 13.416; 3B I : 8.289,
expressed by a single determinantal wave function), the 8.502,9.986, 10.191, 11.590, 12.627.
ground-state energy is lowered by 0.299 ev and by
• For the singlets, oscillator strengths are calculated for transitions from
0.782 ev for starting HUckel MOs and perimeter MOs, the ground state; for the triplets, these are calculated for transitions from
respectively. The oscillator strengths calculated from the lowest triplet state.

10 See, for example, C. C. J. Roothaan, J. Chern. Phys. 19, 1445 16 Wave functions for all other excited states in Table II are
(1951). available.
1114 RUDOLPH PARISER

TABLE IV. Comparison with experiment of Huckel MO calculation

with interaction of all singly excited configurations.

Calculated Experimental-
State E(ev) f E(ev) f
ON <") 0\
OONOO
Nao\O~
lAl o 0 o 0
lEl.l 1.732 0.017 1.79 0.009
8218~ lAll! 3.084 0.002 3.50 0.08
0000 lEI.l
I 4.112 0.116 4.05? ?
lAll! 4.692 1.243 4.52 1.10
O\O\~
<-<")00
lEI .1 5.604 0.365 5.24 0.38
0\'00
<")--
000 5.994
.
<Ii
o
000
I I
6.191
6.867
7.018
0.003)
0.014
0.215
0.278
6.42 0.65

::s 7.018 0.199

a Experimental spectrum is based on Mann, Platt, and Klevens 4 ; the

zero-zero band is estimated for the lowest two excited states,19 and the
other bands are listed according to maximum absorption.

It is clear from inspection of Table II that agreement

between the results calculated from the two different
_NN
1f)0OO sets of molecular orbitals is only fair, even though a
'ON<-
<") _If)
000
considerable amount of configuration interaction has
000 been included. If one were to ignore the ground-state
I I
lowering in the perimeter MO calculation, agreement
for the energies would be better. Nevertheless, the
00
..; relative order of states given by the two calculations is
not always in correspondence.
If)<-O\
Experiment, however, appears to be in very satis-
OO_~_
'00\
<")-
00
00 ~~8 factory accord with the calculation based on Huckel
'0'0 <") NON
00_0 0 ..... 0 MOs both with respect to energy and intensity l7 of
0000 000
I I I I transition. The comparison is made in Table IV. The
.......... calculated intensity for the lowest IAI state appears to
~ <-11)

..
00
000
000
I
N~
NO\ .....

I
be considerably too low, but as Moffitt 6 has pointed out,
this intensity can be readily enhanced through vibra-
tional perturbations. This would add approximately
0.1 to the oscillator strength, that is, just the required
amount. For the lowest lEI state and the two lowest
IAI states the present assignment is thus in complete
agreement with that of Mann, Platt, and Klevens. 4,6
00 _If)
ON~
However, the lEI state at 4.112 ev is predicted to fall
00000\
in between the two lowest IAI states; a hump is present
'"
N C!~~
000 in the absorption spectrum at about 4.05 ev which is
I I I
used for the present tentative assignment. Recent
<")'0<")
experimental work proves that the theoretical assign-
..... ~
oooo
..... 0\
ON
N'ON ment for the two lowest excited singlets is correct,18
000 and there exists indirect evidence that there may indeed
I I I
be a perpendicularily polarized state, i.e., lEI, just above
the lowest excited IAI state. 19 The relationship between
the naphthalene and azulene spectra has been discussed
in detail previously4,6 and will not be considered here.
The location of the triplet states in azulene is not
known experimentally, but the two lowest triplets are
17 No empirical factors are used here to reduce the oscillator
strengths. An empirical correction factor between! and 1 would
o
;g_N ..... improve agreement with experiment. This correction may be due
to polarization of the q electrons.
S .. 18 D. S. McClure, J. Chern. Phys. 22, 1256 (1954).
~~ ~ 19 J. Sidman and D. S. McClure, Symposium on Molecular
Structure and Spectroscopy, Ohio State University, June, 1955.
 STRUCTURE OF AZULENE 1115

TABLE V. Effect of configuration interaction on the lower singlets.

No. CIa Lim. CIb All CI' No. CIa Lim. CIb All CI'
State E(ev) f E(ev) f E(ev) f E(ev) f E(ev) f E(ev) f
Perimeter Mas HUckel Mas

1AI 0 0 0 0 (-0.782) 0 0 0 0 ( -0.299)

lEI 2.710 0.238 2.468 0.086 2.814 0.035 1.742 0.077 1.673 0.042 1.733 0.017
1AI 4.690 1.205 3.626 0.000 4.194 0.003 3.774 0.796 2.937 0.002 3.084 0.002
lEI 4.607 0.405 4.849 0.648 5.095 0.080 4.208 0.382 4.277 0.470 4.112 0.116
1AI 4.629 1.124 5.693 2.845 6.250 1.673 3.835 0.747 4.672 1.892 4.692 1.243

a The corresponding configurations are, upon reading down: ground configuration Vo, V 5,7, V 5,6. V.'.8, and V . . ,7. Vii is the singlet determinantal wave fune.
tion where an electron is excited from the ith to the jth MO; Mas are numbered as in Table I.
b Interaction is included only between the lowest two excited A, and B, configurations.
e Interaction is included among all singly excited configurations. Energies in brackets are relative to the ground configuration Yo. All other energies are
relative to the ground state.

predicted to fall quite close to the lowest excited
singlet j see Table II.
The effect of configuration interaction in azulene is
usually large for configurations which are nearly de-
generate, and for the lower excited states near de-
generacy can be predicted from the conventional simple
LCAO MO theory. This near degeneracy occurs in pairs
among Al configurations. Thus the configuration with
an electron excited from the 5th to the 6th molecular
orbital (see Table I) is of about the same energy as the
one obtained by excitation from the 4th to the 7th
orbital. That these configurations are nearly degenerate
is evident from inspection of the second and eighth
columns of Table V. If one includes interaction only
among those four configurations which are degenerate
in the perimeter model, as advocated by Ham and
Rudenberg,2o one obtains quite satisfactory results for
the lower excited states; see Table V. Interaction
among all singly excited states does, however, give
better results compared to experiment, especially for
the oscillator strengths.
The experimental dipole moment for azulene is about
1.0 D,3 which may be compared to the calculated 7r elec-
tronic dipole moments for the ground state,21 listed in
the second column of Table VI. Configuration inter-
action greatly improves the dipole moment for the
Hiickel MO calculation, making it essentially the same
as the SCF MO result. 8 This should be considered as
satisfactory with respect to experiment, since u-electron
polarization effects would tend to reduce the total
calculated dipole moment. The dipole moments for most
of the excited states (see Table VI) are calculated to be
opposed to the ground state dipole moment. From this
one might expect that polar solvents would shift the
azulene absorption spectrum to shorter wavelengths.
As may be seen in Table VI, the charge densities for
the ground state are in fair agreement for SCF MOs,
perimeter MOs plus configuration interaction, and
Huckel MOs plus configuration interaction. The charge
density at positions 1 and 3 is the largest, and this is
consistent with the tendency of chemical electrophylic
reactions to take place at these positions. 5 ,22,23
The bond orders are brought into good accord by
configuration interaction for the two sets of molecular
orbitals; see Table VI. Application of Coulson's formula
for bond order vs bond distance24 predicts 1.39 A to

TABLE VI. Azulene dipole moments, charge densities, and bond orders, for ground and excited states. 8

State I'(D) d2,2 da ,3 dIO,IO d4, .. d", ds" b... ba,lo b"" b•• , b", bl,II

Ground state:
Perim. MOs, No. C.1. 0 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 0.6472 0.6472 0.6472 0.6472 0.6472 0.0000
HUckel Mas, No. C.1. 6.40 1.0466 1.1729 1.0274 0.8549 0.9864 0.8700 0.6561 0.5956 0.5858 0.6640 0.6389 0.4009
SCF Mas 1.7 0.997 1.049 1.042 0.908 1.034 0.938
Perim. MOs+C.1. 3.36 1.0011 1.1177 1.0157 0.8859 1.0148 0.9304 0.6620 0,6096 0.5915 0.6570 0.64in 0.2828
Hiickel MOs+C.1. 1.88 0.9787 1.0960 1.0132 0.8785 1.0489 0.9482 0.6597 0.6098 0.6108 0.6513 0.6478 0.2882
Exc. states b :
IBI: 1 -1.36 1.1175 0.8548 1.0246 1.0801 0.9275 1.1083 0.6468 0.4316 0.4612 0.6837 0.5936 0.5800
'A,: 2 -2.70 0.8791 0.9985 0.9902 1.0126 1.0770 0.9653 0.5602 0.5267 0.5239 0.5883 0.6024 0.4330
'B,: 2 -1.26 0.7454 1.1627 0.9618 0.9161 1.1626 0.8481 0.5157 0.6062 0.5336 0.5236 0.5917 0.2990
'A,: 3 -1.82 0.8874 1.0323 0.9950 0.9612 1.0894 0.9576 0.5606 0.4964 0.4901 0.6207 0.6002 0.5131
3Bl: 1 -0.86 1.1264 0.8617 1.0363 1.0671 0.9076 1.1280 0.6374 0.4473 0.4748 0.6754 0.5942 0.5713
3Al: 1 0.60 0.9698 1.0416 1.0045 0.9588 1.0464 0.9283 0.5816 0.5113 0.5762 0.5520 0.5947 0.3745

• I' is the dipole moment in Debye, d pp the charge density of the pth atom, and bpq the bond order between atoms P and q: 1 is often added to bp • for the
total bond order. Atoms are numbered as in Fig. 1. Negative dipole moments are opposed to direction shown in Fig. 1.
b Results for excited states are computed via Huckel MOs. For analogous states via perimeter MOs the dipole moments. upon reading down, are: -2.49,
-3.07, -1.72, -7.16, -2.65, and -1.00 D. For identification of states see Table II.

20 N. S. Ham and K. Rtidenberg, J. Chern. Phys. 25, 1 (1956); ibid. 25, 13 (1956).
21 If one assumes a dipole moment for C--H+ of 0.6 D, this would contribute about +0.1 D to the total dipole moment.
22 A. G. Anderson, Jr., and J. A. Nelson, J. Am. Chern. Soc. 72, 3824 (1950).
23 Anderson, Nelson, and Tazuma, J. Am. Chern. Soc. 75, 4980 (1953) .
.. C. A. Coulson, Proc. Roy, Soc. (London) A169, 413 (1939).
1116 RUDOLPH
TABLE VII. The effect of methyl substitution on the lowest
azulene absorption band.
Position 3 4 5 6
AX (mt<) exp -21 41 -17 18 -16
AX (mt<) calc -22 41 -31 20 -25
1.41 A for the peripheral bonds and 1.47 A for the cross
link.25 Bond orders for the excited states, as well as the
charge distributions, are considerably different from the
ground-state values. If one assumes that the vibrational
bond force constants are proportional to the bond
orders, these might be used to consider the displacement
of vibrational bands in excited states.
Application of a perturbation theory enables one to
estimate the spectral shifts in azulene upon methyl
substitution.9 The change in energy difference between
ground state and excited state is then proportional to
the difference in charge density of the two states at the
position of substitution. This calculation for the lowest
lBI state (as obtained through Hiickel MOs plus
configuration interaction) is compared with experi-
ment26 in Table VII. Substitution at the 3 position is
used to calibrate the calculation. The results are on the
average somewhat better than those of previous treat-
ments,27 but not too much significance should be
attached to this. A similar calculation for the second
excited state would predict (see Table VI) hypsochromic
shifts for the 4, 5, and 6 positions and bathochromic
25 E. Heilbronner experimentally estimates 1.45 A for the cross
link, as quoted by C. W. Scherr, J. Chern. Phys. 21, 1582 (1953).
26 P. A. Plattner andE. Heilbronner, Helv. Chim. Acta 30, 910
(1947).
27 See reference 9 for a summary of previous treatments.
PARISER
shifts for the 2 and 3 positions, but experiment appears
to indicate somewhat of a bathochromic shift for all
positions.28 Similar difficulties are encountered for the
strong IAI band at 4.5 ev. However, the present method
for treatment of substitution effects is admittedly crude,
and it does not seem profitable at present to speculate
on the method's shortcomings.
IV. CONCLUSION
It appears evident that the present theoretical
approach is applicable to azulene, a polar molecule,
with about the same accuracy as to naphthalene,14 a
nonpolar molecule. This is most encouraging.
The present calculations also confirm the previous
conclusion,14 namely, that it is important to start with
a reasonably good set of molecular orbitals if interaction
is to be limited to singly excited configurations. In this
connection Huckel MOs are considerably better than
perimeter MOs. This is demonstrated by the results for
the spectrum as well as for the dipole moment of
azulene.
To calculate the spectrum, it is essential to include
interaction among at least the nearly degenerate singly
excited configurations. A general improvement, how-
ever, results from more extensive interaction. This is
particularily true for the dipole moments and oscillator
strengths. However, these still have a tendency to be
somewhat too high, and it may well be necessary to
consider the (]' electrons explicitly in order to account
for this discrepancy between experiment and the
present theory.
28 P. A. Plattner and E. Heilbronner, Helv. Chim. Acta 31, 804
(1948).