Journal of Molecular Structure (Theochem),

151 (1987) 215-222

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FINITE FIELD CALCULATIONS OF MOLECULAR POLARIZABILITY

AND HYPERPOLARIZABILITIES FOR ORGANIC n-ELECTRON
SYSTEMS

G. R. J. WILLIAMS
Electronics Research Labomtoy,
Defence Science and Technology
ment of Defence, GPO Box 2151 Adelaide, S.A. 5001 (Australia)

Organisation, Depatt-

(Received 24 October 1986)

ABSTRACT
The finite field technique in combination with the MNDO molecular orbital method
has been used to calculate the polarizability and first and second hyperpolarizability for
a number of alternant and nonaltemant hydrocarbon systems. The computational advantages of this procedure are examined, and the results obtained from the study are discussed in terms of the electronic structure of the systems under investigation.
INTRODUCTION

Recently, there has been a considerable research effort directed towards

the development of organic and polymeric materials for nonlinear optical
applications [ 11. This interest has arisen from the recognition of the fact
that organic materials with conjugated n-electron systems can exhibit an
extremely large nonlinear optical response. An additional attractive feature
of organic materials is that their structural features may be varied in order
to optimise adjunct properties, such as thermal and mechanical stability,
whilst still maintaining the electronic interactions responsible for the nonlinear optical effect. In order to provide some guidance to experimental
efforts in this area, it is therefore of some interest to investigate practical
computational techniques for the calculation of molecular hyperpolarizabilities of conjugated ~-electron systems.
Two main approaches for the calculation of molecular hyperpolarizability
(and polarizabihty) are possible. In the first, the new ground state wavefunction is calculated directly by a variational method in the presence of a
perturbing electric field. In the second, a perturbation expansion in terms
of the excited states of the unperturbed system is used. In either case, the
underlying quantum chemical problem may be treated by any of the currently available semiempirical or ab-initio methods.
The combination of the semiempirical MNDO molecular orbital method
[2] and the finite field technique [ 3-71 offers the advantage of allowing
the simultaneous calculation of all appropriate tensor components of the
0166-1280/87/$03.50

0 1987 Elsevier Science Publishers B.V.

216

polarizability
(ar) and first and second hyperpolarizabihty
(p and 7; respectively) for large organic molecules, with a moderate computational
effort.
This means that the method may be routinely
applied, in a systematic
manner, to investigate nonlinear optical characteristics
of organic systems
that may be selected as potential
candidates
for application in the nonlinear optics area.
In this paper we investigate the application
of this procedure
to the
calculation
of polarizability
and hyperpolarizabilities
for a series of alternant and nonalternant
hydrocarbons
having between 3 and 7 conjugated
n-bonds.
Ab-initio
calculations
of polarizabibty
and hyperpolarizability
have
generally been confined to studies of smaller molecular systems [B--10].
Previous finite field calculations of the first hyperpolarizability,
p, have also
been reported for a number of smaller molecular systems [5, 71. For larger
systems, p has been obtained by a combination
of the semiempirical CNDO
method and traditional
perturbation
theory [ll, 121, but in these latter
studies no calculation
of the second hyperpolarizability
has been reported.
Values for p and 7 have been obtained for some monosubstituted
benzenes
by Zyss [ 131 using the INDO method. However, for large conjugated n-electron systems, the calculation of p and 7 has generally been confined to computing only the Ir-electron contribution
to these tensors [3]. In the present
study, both u- and n-electrons are explicitly included in the calculations.
THEORY

The energy of a molecule

power series as

in an external

W(E) = W(0) --/.~ioEi - (2!)-

cij Ei Ej - (3!)-

field, E, may be written

in a

flijk Ei Ej Ek

-(4!)-7ijklEiEjEkEl--e.

(1)

where summations over repeated indices are assumed. pi0 is a component of

the permanent dipole moment, oij is a tensor component of the polarizability and flijk, Yijkl are components of the first and second hyperpolarizability,
respectively.
A component
of the total dipole moment, pi(E), is obtained from the
derivative (a W/aEi)
pi(E)

= ,Uio + &ijEi + (2!)-

flijk EiEk f (3!)-

7ijklEjEk

El + e e e

(2)

The coefficients
aij, flijk, Yijk[ in eqns. (1) and (2) may be obtained either
from perturbation
theory or by using a finite field method. Chosing the
finite field method one may write the perturbed Hamiltonian for the molecule as [8]
H = N--

x
i

E-r(i)

(3)

217

Where E is a finite electric

electron.
Following
a variational
term results in a modified
elements [ 41
Fllv=

FLv +

C
i

EiDLv

field and r(i)

the position

operator

for the ith

Hartree-Fock
procedure,
this perturbation
form for the standard Hartree-Fock
matrix
(4)

where ppv is the unperturbed

Hartree-_Fock
matrix element, Ei is the ith
of the dipole
component
of the finite field and Dbv is the ith component
moment matrix element. In this work the F-matrix elements defined in
eqn. (4) have been calculated in the MNDO approximation
[ 21.
From the resulting perturbed
wavefunctions,
the dipole moment pi(E)
defined in eqn. (2) was obtained. The tensor components of (Y,0 and r may
be obtained from eqn. (2) by successively computing
pi(E) for a series
of positive and negative electric field strengths of the same magnitude.
Alternating the sign of the applied field allows the elimination of all even
or odd terms in the expansion. This ensures that the contamination
from the
next higher term of the power series is completely
removed, leaving only
the next higher term of the same type (even or odd) contributing.
At the
field strengths used in this work (+5 X 10m3 to +2 X lob2 a.u.) it means that
the contribution
from the next higher term is approximately
four orders of
magnitude smaller than the tensor element being determined.
In the case of
0, it is possible to explicitly eliminate the next two higher terms on the
expansion,
resulting in a contamination
term approximately
six orders of
magnitude smaller than the 0 tensor element being determined. A procedure
similar to that described above was used by Bartlett and Purvis [8] to obtain
(II, 0 and y components
from the energy expression (eqn. 1) in their abinitio studies of small molecules. We have preferred to work with eqn. (2)
instead of the energy expression, as it has the advantage of reducing the field
dependence
of the expansion coefficients
by a power of E. By carrying out
the necessary algebraic manipulations
it is possible to obtain from eqn. (2)
general expressions for a, 0 and 7 tensor elements in terms of pi(E) for any
molecular system, independently
of any specific molecular symmetry considerations.
These general expressions
are given in the Appendix to this
paper. Previously
reported
[13] formulae based on eqn. (2) have been
restricted in their applicability to molecules of specific symmetry types.
CALCULATIONS

The unperturbed
using the MOPAC
code required to
tensor components
MOPAC program
carried out on a
system.

MNDO Hartree--Fock
matrix elements were computed
[ 141 molecular orbital program. The additional computer
carry out the finite field calculations and to evaluate the
of (Y, P and y was developed, and incorporated
into the
as a set of additional subroutines.
The calculations were
IBM 3033 computer
system running the MVS operating

218

The molecules selected for study in this work are shown in Fig. 1 together
with their point group symmetry and the local axis system chosen for the
calculations. All molecular geometries were optimized using the MNDO
procedure before carrying out the finite field calculations.
In addition to the Cartesian tensor components (Appendix) we have also
computed the mean (isotropic) values for these tensors, defined by the
expressions [ 151
(01)= l/3 (QX +
(B) =

ayy

CYZZ)

3/5 (Pyyy + Pyxx + pyzz) (y = major symmetry axis)

(7) = l/5 (YXXXX+ ryyyy

+ rzzzz

+ 2rxjcyy

DISCUSSION

Previous MNDO finite field studies on a number of molecular systems

[5] have demonstrated the ability of this technique to calculate, with
reasonable accuracy, values for molecular polarizability and first hyperpolarizability. However, in these latter studies no values for the second
hyperpolarizability were reported. In order to determine the ability of the
MNDO finite field procedure to calculate the sign and magnitude of 7, we
have computed the mean value of the second hyperpolarizability for the
molecules CF4, CCL, and benzene, where experimental values are available
for comparison with the theoretical results. These are presented in Table 1.
In the case of CF4 the present theoretical result is in close agreement with

Fulvene

Benzene

Heptafulvene

Fulvalene

(c2)

(6,)

(c2v)

(2,)

\--I
I
I

8
Naphthalene
2,)

Sesquifulvalene
IC2v)

biphenyl
2,)

heptafulvalene
2,)

Fig. 1. Axis system and symmetries of alternant and nonalternant hydrocarbons.

219
TABLE 1
Calculated and experimental values for mean y (1O-36 e.8.u.)
Molecule

Calculated

Experimental

CF.
ccl,

0.14
0.70

o.14a
2.0b

C, H, (benzene)

0.74

aRef. 18. bRef. 19. Static value, ref. 16. dat 694.3 nm, ref. 20.

the experimental
value, although
this is most probably
fortuitous.
The
calculated values for carbon tetrachloride
and benzene are smaller than the
observed values, but are of the correct order of magnitude and sign. The
present MNDO result for benzene, 0.73 X lo-36 e.s.u. is within 25% of the
recently
published
result of Shelton
[16] who obtained
a value of
0.98 X 1O-36 e.s.u. for the static (X = -) value of the second hyperpolarizability of benzene. In the case of CCL,, the presence of the second row elemment chlorine introduces an extra factor into the calculation as the present
MNDO method may not be fully optimal for some molecular properties of
molecules containing elements of the second row of the periodic table.
In Table 2, the principal tensor components
and mean values of the polarizability and hyperpolarizabilities
are presented for the molecules studied.
A number of features are evident on examination
of Table 2. In the case of
benzene, the molecular symmetry requirements
axx = cuYy, yxxxx = yYYYY
= 113 Yxxxx are taken into account within acceptable numerical accuracy
limits. For the Dbh and DZh systems, all values for the 0 tensor vanish by
symmetry.
A number of more general trends are also evident from the
results.
In addition
to the expected
increase of polarizabihty
with increasing
molecular size, the calculations also show that the predicted mean polarizability for the nonalternant
hydrocarbons
is always larger than for the corresponding alternant hydrocarbon
isomer.
Molecules with a large first order hyperpolarizability
give rise to large
second order susceptibilities
xZ in non-centrosymmetric
crystals. Such
materials are useful in a variety of electro-optical
devices, such as the Pockels
cell. The molecules included in these studies with nonvanishing p values are
those belonging to the CZV point group: fulvene, heptafulvene
and sesquifulvalene.
Both heptafulvene
and sesquivulvalene
are predicted
to have
negative mean fl values, with sesquifulvalene
having the 0 value of largest
magnitude. Fulvene is predicted to have only a relatively small positive mean
value of 0.
The second hyperpolarizability,
7, is of particular
importance when considering materials which may exhibit large electronic Kerr effects. The polydiacetylenes
have received considerable
recent attention
in this context.

69.1
69.1
8.2
48.8
7.2
0
0
0
0
0,
1883
1815
6
681
533
542
1443
0.73

48.8
100.5
8.9
52.8
7.8
9.8
49.0
-7.5
30.8
2.7
12818
-1750
7
-537
790
337
2451
1.23

aIn4$3.b
In 1Om3'e.su
. . 'In 1O-"6e.8.u .

(-Y)
(7P

7ZZXX

PYYY
Pyxx
PYZZ
(P)
cpP
rxxxx
TYYYY
~%ZZZ
TXXYY
-fYYZZ

Qxx
QYY
%z
C(Y)
(CUP

gH6-jy

80.2
142.4
11.7
78.1
11.6
-251.1
-59.2
3.7
-184.0
-15.9
7156
631
-2
14957
969
533
8140
4.10

Calculatedvalues
fora,pandy (inatomicunits)

TABLE2

105.9
149.8
13.3
89.6
13.3
0
0
0
0
0
14985
42625
25
752
1222
685
12590
6.34

goHag

78.0
208.1
14.5
100.2
14.8
0
0
0
0
0
19248
41664
9
8233
1112
521
16130
8.12

110.9
286.8
17.1
138.3
20.5
-1720.3
-285.4
24.6
-1188.7
-102.7
15839
39635
17
27415
1053
645
22743
11.45

~c2Ho-$

125.9
186.9
15.9
109.6
16.2
0
0
0
0
0
2732
267611
32
-3039
2061
851
54024
27.20

140.9
369.5
19.8
176.7
26.2
0
0
0
0
0
8173
60464
2
58135
1391
850
37879
19.10

221

For the molecules studied in this work, the computed mean value for 7
generally shows an increase with increasing n-conjugation, which is not
unexpected on the basis of simple theory considerations [ 171. However,
the particular nature of the n-electron structure is obviously important, as
is evident in the predicted value of (7) for biphenyl. The biphenyl molecule
has a calculated (7) value of 27 X 1O-36 e.s.u., which is considerably larger
than that predicted for the other molecules, including the seven n-bond
system heptafulvalene. The n-electron structure of biphenyl is characterised by the presence of two distinct aromatic n-systems separated by a
C-C single bond, in contrast to the other five, six and seven n-bond sy,sterns investigated in this work. Further work is in progress for the calculation
of 7 for other related n-systems.
CONCLUSION

This study indicates that the MNDO molecular orbital method in combination with the finite field technique provides a practical computational
procedure for the investigation of molecular polarizability and hyperpolarizability of organic materials with possible nonlinear optics applications.
ACKNOWLEDGEMENT

The author would like to thank Dr R. C. Haddon (AT & T Bell Laboratories, Murry Hill, NJ) for making available a copy of the MOPAC molecular orbital program.
APPENDIX

Tensor elements for (Y,p and 7 in terms of computed values for pi(E)
QiiEi = 3 [pi@i) -Pit--Ei)l -*
QijEj = 3 [pi(Ej)-Pi
PiiiEf=

eEj)l

4 [pi(Ei) + Pi(

/3ijjEi= 4 [pi(Ei) + pi(-Ej)]

-[pi

rijjjEj=

-[~i(Ej)-_~(-Ej)l

YjiiiEz = -[Mj(Ei)

riijjEiEi= 4IPi

-h-C~i(mj)

-Hi(-zj)I

-13

IPi

-&

[Pi(iZj) +

-CC~ (--Ei)l

riiiiE!=

[Pi(2Ei)-/4i(-2Ei)l + OtE)

-/-tj(-Ei)l

tii(--2Ei)I -3 I-cio+ 0 (6)

Pi(-wj)I

-?Pjo + 0 (6)

+ 1bi(2&) -Pi(--2Ei)I + 0 (6)

+

f[~i(2.Ej)-~i(--2Ej)I + 0 (e)

+ 1 IPi

-Pj(--2Ei)I + 0 (~1

-/~i(+Ji)l + [Pi(Ej) -Pi(-~j)I

3[pi(Bj) -~i(-~j)l

+ 0 (~1

+ 4bitEi, mj) -~i(-Ei, --2Ei)I

-[~i(Ei,Ej)-~i(-Ei,-_Ei)l

+ 0 (~1

222
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