Volume 171, number 3 CHEMICAL PHYSICS LETTERS 3 August 1990

Nonlinear optical properties of organic solids:

ab initio polarizability and hyperpolarizabilities
of nitroaniline derivatives
Chantal Daniel ’ and Michel Dupuis
Department 48BMS 428, Data System Division, IBM Corporation, Neighborhood Road, Kingston, NY 12401, USA

Received 16 April 1990

The static dipole polarizability, first and second hyperpolarizability tensors of molecules with nonlinear optical characteristics
are calculated via ab initio coupled-perturbed Hartree-Fock theory. A study of the effect of basis set augmentation on the calcu-
lated properties for the nitrobenzene molecule emphasizes the importance of diffuse functions. The method is then applied to a
series of methyl substituted nitroanilines, and comparison with existing experimental data and other computational data is pre-
sented. The results indicate that the present approach works well to reproduce experimentally observed trends.

1. Introduction yet improved nonlinear optical (NLO ) character-

Materials with suitable nonlinear responses to in-
cident light can be exploited to alter propagation
characteristics such as frequency, amplitude or phase
of the transmitted electromagnetic radiation. These
materials provide the means to tailor the nature of
light to suit particular applications [ 11. In this con-
text progress in the development of many technol-
ogies such as optical information processing, tele-,
communications, integrated optics, optical comput-
ers, laser technology, .... depends ultimately on the
molecular properties of constituent materials. In re-
cent years much attention has been given to organic
compounds, in view of their unusual large nonlinear
response. This characteristic feature is attributed to
the large polarization of the delocalized n electron
cloud. The best known and studied compounds are
the urea crystals and the nitroaniline derivatives.
Numerous other organic materials have been syn-
thesized and their polarizability characteristics de-
termined. An understanding of the relation between
molecular structure and polarizabilities is emerging
which may lead to the discovery of materials with
’ Permanent address: ER 139 du CNRS, Institut le Bel, 4, Rue
Blaise Pascal, 67000 Strasbourg, France.
istics. Theoretical computations of molecular polar-
izability have the potential to help greatly in facili-
tating the design of new NLO molecules.
A theoretical approach to molecular engineering
for NLO involves three distinct stages: (a) selection
of a formalism, and computer implementation of the
equations; (b) benchmark calculations to establish
a level of reliability of the model through compari-
sons with available experimental data; (c), predic-
tive calculations of the properties of interest prior to
synthesis for a series of molecules followed by syn-
thesis of the most promising candidates. We recently
reported the implementation of the equations for the
computation of molecular (hyper )polarizabilities in
the limit of a static field using the coupled-perturbed
Hartree-Fock formalism (CPHF) based on ab initio
SCF wavefunctions. We showed that NLO studies
using this approach are feasible even for large mo-
lecular systems when taking advantage of the ex-
tended computational resources of today’s super-
computers [ 21. Initially we applied the method to
conjugated polyenes from C4H, to CZ2HZ4.For the
shorter molecules experimental data is available, and
therefore we were able to study carefully the basis set
requirements for a reliable determination of the po-
la&ability tensor cyand of the hyperpolarizable ten-

0009.2614/90/$ 03.50 0 1990 - Elsevier Science Publishers B.V. (North-Holland) 209

Volume 17 1,number 3 CHEMICAL PHYSICS LETTERS 3 August 1990

SOTy. It was found that the present approach based

on the SCF model reproduces the (Ytensor rather
well, and that for y a significant absolute error re-
mains, which presumably can be attributed to the ef-
fects of electron-electron correlation not taken into ‘Nc,kl&jk/( -w; 01) w2, w3) , (4)
account in the SCF model. Although differences with where Nis the number of molecules per unit volume
published values based on semi-empirical theoreti- and C’,, and C’ijk,describe the local field corrections,
cal approaches [3,4] were not discussed in that pa- are used to extract polarizabilities from measured
per, we noted that discrepancies between ab initio susceptibilities. These may represent an oversimpli-
and semi-empirical a! and y values are quite signif- fication depending on the frequency dispersion and
icant. To further our appreciation of the quality of on the vibrational effects. In the present work we will
ab initio SCF determined (hyper )polarizabilities, we compare the calculated average static first hyper-
decided to calculate these properties for systems for polarizability /$.,,( 0; 0,O) to the measured quantity
which experimental data is available, specifically the &,, ( - 2~; w, w ) extracted from solution phase elec-
nitrobenzene molecule and some nitroaniline tric-field-induced second-harmonic generation
derivatives. (EFISH) experiments:
The interaction of light, or other electromagnetic
fields, with a molecule polarizes the charge distri- BYec(-20;0,LC))=(P:+Bf+P:)“2, (5)
bution and alter the propagated field. The micro- where pi is given by
scopic polarization P induced along the i axis in a
molecule by local electric fields Ej,
Ek,and Elapplied PC = 4 ki, (8,kk + PkBklk
+ h&i) 9 i=l,2,3. (6)
in the j, k,and I directions respectively is given by
Actually EFISH measurements are interpreted as an
jkl
J jk electric field nonlinearity due to an effective third-
(1) order susceptibility
The linear response to the field is described by the
(7)
molecular polarizability (Y+while the nonlinear re-
sponses which are exploited in nonlinear optical de-
vices, are described by the molecular hyperpolariz-
YEFISH(-2W; QJ,Q4 0)
abilities. In the present work we concentrate our
attention on the first and second hyperpolarizabili- =T(-2w;w,w,O)t/@(-2w;w,w)/SkT. (8)
ties, Biikand rzjk/ respectively. The measured prop-
Very little information is available in general for
erties are actually xi” (w), @ ( -co; ml, w2), and
y( - 2~; w, w, 0), which is therefore neglected in the
x$J( -co; w,, wz, w3), the frequency dependent
interpretation of experiments. A unique contribu-
macroscopic first-, second-, and third-order suscep
tion of theory could then be to predict the electronic
tibilities respectively, where o is a linear combina-
polarizability term 7 and thus to contribute to im-
tion of the frequencies, wI, w2, and o3 of the oscil-
proved interpretations of experiments. And indeed,
lating fields. These quantities enter into the
from a computational point of view, the calculation
macroscopic polarization induced by oscillating ex-
of y’s is not much more difficult than that of pLs.
ternal fields in a array of molecules through the
Though the EFISH technique has been gradually im-
equation
proved, great care must be taken for both the dipole
Pi= C~b"Ejt C x~~'EjE~,t
C x~~EjEkE,t...
. moment determination. and hyperpolarizability
i ik jkl
measurements, and solvent effects must be consid-
(2)
ered. For instance, at the same frequency, the mea-
The relationships between the molecular hyperpo- sured first hyperpolarizability for p-nitroaniline BVec
larizabilities J and y and the crystalline susceptibil- may increase by a factor of two going from dioxane
ities x(2’ and xc3), to methanol [ 5,6 1. In any case extensive studies may

210
Volume 17I, number 3 CHEMICAL PHYSICS LETTERS
be required on a systematic set of organic molecules
to calibrate the accuracy of quantum mechanical cal-
culations. Finally it is important to keep in mind that
the experimental quantities are frequency dependent
and that the formalism used in this study does not
take into account frequency dependence.
Several theoretical approaches to calculating mo-
lecular nonlinear optical properties have appeared in
the literature. They differ first in the form of the mo-
lecular wavefunction which defines the ingredients
from which the nonlinear optical properties .are cal-
culated, i.e. the electron density and its changes in
the presence of an electric field. Simple and attrac-
tive approaches are the semi-empirical model Ham-
iltonian methods such as the all-electron CNDO
model [ 7 ] or the n-electron-only PPP model [ 8 1.
Owing to their computationally inexpensive char-
acteristics these methods can be relatively easily ap-
plied to larger molecular systems [ 5,9-l 31. First
principles methods deal traditionally with smaller
molecules because of their greater computing re-
quirements. They have however the potential to pro-
vide results of a more reliable nature. The second
difference among theoretical approaches lies in the
manner in which the nonlinear response is calcu-
lated in the framework of perturbation theory, either
by means of the CPHF approach [ 2,3,13 ] or the sum-
over-states (SOS) approach [9-l 21. Especially rel-
evant to the research presented here are the recent
calculations of /3and y reported by Morley et al. [ 12 ]
for the same systems as the ones investigated here.
We note that because of the size of molecules con-
sidered here these authors must resort to a drastic
0
/N\ 0
NI TROBENZENE PNA
Fig. 1.
3 August 1990
truncation of the sum over states. The results are
critically dependent on the level of truncation and
thus the computational procedure does not appear to
be well defined at the present time.
Relatively few ab initi calculations of (hy-
per)polarizabilities have been published, and most
have dealt with small molecular systems [ 14,15 1. In
this paper we report on the calculation of these prop-
erties for larger systems which have been the subject
of numerous experimental investigations, in panic-
ular we present the results of calculations of these
properties for methyl substituted nitroanilines per-
formed in the framework of the Hartree-Fock SCF
theory using extended basis sets. The properties of
interest were evaluated from analytic expressions for
the derivatives of the SCF energy with respect to an
electric field, obtained through CPHF theory. Sec-
tion 2 of this paper gives the most important tech-
nical details related to the calculations. The basis set
dependence of the calculated properties for nitro-
benzene is described in section 3. This study resulted
in the selection of a basis set used for the calculations
on nitroaniline derivatives which are discussed in
section 4. Conclusions are given in section 5.
2. Computationaldetails
The molecules considered in this work are shown
in fig. 1 along with the system of Cartesian coordi-
nates adopted. All geometrical parameters of aniline,
nitrobenzene (NB), and p-nitroaniline (PNA) were
/N\ 0
0 a
/N\ .YN\ 0
0 0
UNB DUNE MNA
211
Volume I7 1, number 3 CHEMICALPHYSICSLETTERS
optimized at the SCF level of theory using a (9s,Sp) /
[ 3s,2p] double-zeta quality basis set for the second
row atoms and a (4s) / [ 2s ] double-zeta basis set for
H. This basis set is denoted DZV thereafter [ 161.
The geometry of the nitroaniline derivatives o-
methyl-p-nitroaniline (MNA), p-N-methylamino-
nitrobenzene (MNB), and pN,N-dimethylaminon-
itrobenzene [ 61 borrowed parameters from the op-
timized geometry of pnitroaniline, with “idealized”
methyl groups substituted for the H atoms where ap-
propriate. For nitrobenzene and p-nitroaniline the
calculated structures are in overall excellent agree-
ment with experimental structures. For this latter
molecule the (hyper)polarizability tensors calcu-
lated at the theoretical geometry and at the experi-
mental geometry showed no significant differences.
Therefore we are confident that the conclusions based
on the present study would hold, had we used slightly
“better” geometries.
Detail of the equations and their computer imple-
mentation in the program HONDO [ 171 can be
found elsewhere. The calculations were performed
on the LCAP-2 and LCAP-3090 computer systems
[1X1*
Before describing the computational results, we
must underscore the fact that the calculated tensors
/I and y reported throughout this paper are in accord
with eq. ( 1). They are divided by a factor of 2 and
6 respectively from the values printed by the com-
puter program HONDO. This is due to a difference
in definition used by experimentalists which follow
the Bloembergen model [ 191 and by theoreticians
who follow the SOS approach, both of them based on
a perturbation expansion of the energy and of the in-
duced polarization (eq. ( 1)) on the one hand (the
numerical factor in front of the term at order n is l/
n, and theoreticians which adopt the CPHF ap-
proach based on a Taylor series expansion of the en-
ergy on the other hand (the numerical factor in front
of the term at order n is 1 /n! ). For the sake of com-
parison with already published experimental data,
we report tensor values properly scaled to the Bloem-
bergen model.
3. Basis set effects for nitrobenzene
The choice of basis set is of paramount impor-
212
3 August 1990
tance in ab initio calculations of NLO properties. It
is now generally accepted that energy-optimized ba-
sis sets which yield satisfactory geometrical param-
eters in molecular structure determination need be
augmented with diffuse functions for a more flexible
description of the electron density away from the nu-
clei. For small molecules the basis set dependence of
the calculated properties is already well documented
[ 2,141. For larger molecules it is currently believed
that functions on other centers may lead to an ad-
equate description of the polarization effects asso-
ciated with a given center. Until recently no com-
putational evidence of this hypothesis was available.
The effect of basis set augmentation on the calcu-
lated properties for large systems was first explored
for polyenes C4H6 to CzzH2+ For short polyenes ex-
tra diffuse functions and diffuse polarization func-
tions are crucial for describing the second hyper-
polarizability. However for the longer chain the
importance of diffuse functions are notably reduced.
We are concerned here with the effect of the basis
set augmentation on the calculated polarizability, first
and second hyperpolarizabilities for the nitroben-
zene molecule. Starting from the double-zeta quality
basis set used for the geometry determination, we
added up to three diffuse functions on the second-
row atoms of p and/or d type. No diffuse functions
were appended to the double-zeta basis set for the
hydrogen atoms. This choice was made since we are
concerned with the effects associated with the out-
of-plane Kelectrons mainly. In doing so we sacrificed
somewhat the accuracy of some of the components
of the polarizability tensors. The fact that the pzII
component dominates all other quantities entering
the observable Bv,, and that the diagonal component
yzzzzis very much larger than any other component
of the y tensor provides a justification of this choice.
Our previously published results on C4H6 suggested
that (Yand /3 should not be affected too much by the
lack of diffuse functions on the hydrogen atoms. It
is worth remarking that we have not explicitely in-
cluded diffuse s functions. This is because we make
use of Cartesian Gaussian functions. In doing so a
single exponent cd is associated with six functions,
live of the 3d type and one of the 3s type. The radial
part of the latter one has a maximum in the region
where a 1s function with exponent csx2.Old would
have its maximum. Therefore some of the basis sets
Volume 171, number 3 CHEMICAL PHYSICS LETTERS 3 August 1990

described below include diffuse s functions implic-
itely. The Gaussian exponents of the diffuse func-
tions for the second row atoms were varied in a dis-
cret manner to check the importance of diffuseness
of the functions. Ultimately we wanted to select a
basis set which would offer a satisfactory compro-
mise between size and quality.
The individual independent components along the
Cartesian axes of the (hyper)polarizability tensors
calculated with different basis sets are given in table
1. The notation adopted indicates which functions
are appended to the DZV basis set to form bases A
through I. The exponents of the additional functions
are given next to their types. It is striking to note that
for a! and /I the various basis sets yield very similar
results. The diffuse functions affect most aY,,and fl,,,,=,
which happen to be the smaller components in mag-
nitude. The CX, and CL components, and the mean
value & change by at most 15%. Even the DZV re-
sults are satisfactory. This may be the most vivid il-
lustration yet of how basis functions on neighboring
atoms help in describing the polarization of the va-
lence electrons. The same conclusion applies to the
/I tensor. The components jxxz and jl~~~are relatively
insensitive to the basis set. The quantity AM is how-
ever sensitive to the basis set owing to the negative
sign of /I211which enters its definition.
In contrast at least two diffise d-type functions ap-
pear to be necessary to obtain satisfactory values of
y. Basis sets A through D have no or at most one dif-
fuse d set. Basis sets E through I have two diffuse d
functions. The components Y,-_, rxxyv,y===,yW and
ryvzzhave dramatically different values for bases A
to D than for bases E to I, some differ by more than
one order of magnitude. This is not the case for JJ====,
which happens to be the largest component of them
all. Again we attribute this behavior to the cooper-
ative effects of neighboring basis functions. The end
result however is a mean value 7 which reaches a sec-
ond plateau with bases E through I. Somewhat sur-
prisingly though, the inclusion of a tight d function
appears to result in a slightly smaller mean value of
jIYecand y. The diffuse p function added to set E to
create set I has also a marginal effect. Clearly we do
not observe basis set convergence for the properties
of interest. However in accord with our previous

Table 1
Nitrobenzene (hyper)polarizabilities: basis set dependence

A B C D E F G H I

DZV Id Id 2d 2d 2d 2d 3d 3d lp,2d
d-8 d.2 d.8 d.8 d.2 d.2 d.8 d.8 p.05
d.2 d.15 d.05 d.015 d.2 d.15 d.2
d.015 d.085 d.015

P .) 6.0 5.5 5.6 5.3 5.4 5.6 5.6 5.4 5.4 5.6
%z b) 13.0 13.0 13.5 13.6 13.7 14.0 13.7 13.7 14.0 14.0
%Y 4.3 4.8 6.4 6.5 6.9 7.1 6.9 7.0 7.2 7.1
t&z 13.7 14.2 15.3 15.4 15.6 15.8 15.5 15.7 15.9 15.7
a! 10.3 10.7 11.7 11.8 12.1 12.3 12.0 12.1 12.3 12.3
/%xzC~ 48.3 41.7 38.5 37.0 38.1 45.4 42.3 40.1 43.4 43.2
Bw* 5.0 4.1 5.8 6.2 8.3 16.9 16.7 16.8 15.5 20.3
- 143.2 - 127.3 - 134.7 - 139.8 - 141.3 - 127.8 -131.4 - 142.7
k - 138.5
90.2 -117.3
71.5 104.6 84.1 88.3 94.4 99.0 70.9 72.5 99.5

Y- d) 33.9 55.4 145.6 159.4 222.9 631.6 448.6 446.3 524.2 564.6
YWY 45.6 41.0 60.6 66.6 92.7 300.4 294.6 289.3 234.2 327.8
Yzw -75.8 -60.4 -18.6 - 10.4 12.3 123.1 100.3 96.1 97.6 109.4
YYJW 46.7 38.9 72.8 77.3 123.4 632.9 795.9 751.0 414.8 725.5
VW,, 23.3 22.8 44. I 49.5 72.5 244.7 267.7 259.6 189.5 250.5
Yz. 2051.5 1709.9 1920.6 1748.3 1923.7 2591.8 2460.7 2250.2 2354.5 2565.3
P 423.7 362.2 462.2 439.3 525.0 1038.6 1006.1 947.5 867.2 1046.2

213
Volume 17I, number 3 CHEMICAL PHYSICS LETTERS 3 August 1990

work [2], the very distinct plateaux of calculated
values are sufficient for our purpose of defining a ba-
sis set of semiquantitative accuracy which should
make it possible to differentiate substituent effects in
chemical structures.
The present results combined with our earlier
findings for the polyenes suggest that basis set E with
a diffuse d function and another very diffuse one
constitutes a satisfactory compromise between size
and quality. A slightly smaller basis set would have
been sufficient, had we limited our research to the
calculation of (Y and /3. The calculations reported
thereafter were carried out with basis set E.
4. Application to nitroaniline derivatives
To establish the level of reliability of ab initio SCF
derived (hyper )polarizabilities, we calculated these
properties for aniline, PNA, MNA, MNB, and
DMNB using the basis set denoted E. The results are
gathered in table 2 along with some available ex-
perjmental data from refs. [ 5,6,20].
We first note that the SCF calculated dipoles are
in excellent agreement with experiment, except for
the PNA value which is somewhat too large. The
agreement for & is also excellent, and these results
contribute to the general belief that the ab initio SCF
methodology is able to predict dipole polarizabilities
with a high degree of accuracy. The calculated &
values extracted from eqs. (5) and (6 ) show some
interesting trends as well: for aniline and nitroben-
zene, IL, is small; for PNA and its methyl substi-
tuted derivatives aec is much larger although they
appear to be a factor of 2 to 3 smaller than the ex-
perimental values measured at a wavelength of 1.9 1
pm. The jj values are found to be in qualitative ac-
cord with experiment [20] although their absolute
values are in error by a factor z 5. We note that these
results are in line with calculations recently reported
for benzene for (Yand y [ 2 I], and for the haloform
series CHX3 for (Y,/?, and y also reported recently
[ 23 1. For the haloform series, the calculated values
of p were found to be z l/6 the experimental value.
We note that 7 shows a behavior which parallels a,,.
The mean value of y for PNA and its derivatives are

Table 2
(Hyper)polarizabilities ‘) of benzene derivatives

Benzene Aniline NB PNA MNA MNB DMNB

0.0 1.6b’ 5.2 6.1 7.6 7.3 7.1

10.0 12.5 12.3
0.0 9.6 9.5 19.6 19.5
1.4 2.0 16.9 16.7
3.8 5.7 5.4
0.0 1.5”’ 5.6 8.2 8.2 8.5 8.8
9.3 11.3 12.3 14.3 16.1 16.2 18.2
0.0 1.1 1.0 4.4 4.8 6.0 7.8
1.3 1.3 1.0 2.0 2.2 2.5 3.2
0.9*’
1.4 4.1
1.5 6.3
8.0 6.8

1.4 1.5 15.5

1.7” 3.9 7.9

2.4 1.1 12.3

5.7f’
1.7

a) p in D, a: in A’,p in I 0m30esu, and y in 1O-36esu. b, Experimental data from refs. [ 5,6,20].

c, This work and data from ref. [ 2 11. A slightly different basis set was used for benzene, so that the data is not fully consistent throughout
the series. The conclusions are unchanged however.
c) Datafromref. [9,10]. “Datafromref. [22]. 8)Datafromref. [lo].

214
Volume 171, number 3 CHEMICAL PHYSICS LETTERS
at least twice as large as for aniline and NB. The in-
cremental factors for 7 are not as large as forjIvecwhen
going from PNA to DMNB.
The key ingredients for large fl are well under-
stood: they are linked to the presence of a “donor”
group and of an “acceptor” group in the molecule
which result in a highly polarizable system. Aniline
and nitrobenzene are lacking one of the two, and
therefore their j? values are small. This is observed
experimentally for p and the present calculations are
in accord with this notion. Nitroanilines contain a
donor and an acceptor group, they have large /3’soh-
served experimentally and again the present calcu-
lations reflect this fact. The present study suggests
that the same ingredients contribute to large y values.
In table 2 we collected also other calculated values
previously published and obtained with the PPP and
CNDO/S methods. We note that great care and cau-
tion must be used when comparing data, as the pub-
lished data do not appear to be always consistent.
See for example refs. [ 9, lo] _The values listed as PPP
are taken from ref. [ lo]. However we note the sen-
sitivity of the PPP results on the choice of the PPP
parameters, as the jl values may vary by as much as
a factor of two. The SCF method used in this work
and the PPP method yield similar results for aniline
and nitrobenzene, while the j$, for nitroaniline is
significantly larger than for PNA using the PPP
method. The CNDO/S values listed in table 2 are
taken from refs. [ 11,221.
5. Conclusions
To the best of our knowledge this study represents
the first attempt to calculate the (hyper)polarizability
tensors of experimentally well studied organic mol-
ecules by means of a method based on ab inito SCF-
LCAO formalism. The trends extracted from cal-
culatedb, (Y,8, and y are in accord with experimental
observations. We note however that calculated j?“,‘s
are not quite within a factor of 2 of the experimental
data, and that calculated y’s are x 5 times too small
consistently. While this finding is somewhat disap-
pointing, it is in line with results obtained for other
molecules using the same approach. Of course com-
parison was made between experimentally measured
frequency dependent properties and calculated static
3 August 1990
properties. Using the approach described in ref. [ 15]
it will be possible to remove this part of uncertainty.
Computed frequency dependent (hyper)polariza-
bilities for some of the same molecules will be re-
ported in a future publication.
Finally we note a potential unvaluable contribu-
tion of these and similar studies to the interpretation
of experimental data. Traditionally, the second hy-
perpolarizability contribution to EFISH measure-
ments is ignored when extracting b, This is because
there is often no knowledge of the order of magni-
tude of y which is then ignored. Calculations of the
type described here, by yielding values of y may help
improve the interpretation of experimental data.
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