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AM1 study of the relationship between the donoracceptor strength

and the polarizabilities of pushpull polyenes

Published on 01 January 1998. Downloaded on 17/12/2014 03:47:10.

Yinghong Sheng,a Yuansheng Jianga* and Xiao-Chuan Wangb

a Department of Chemistry, Nanjing University, Nanjing 210093, China
b Molecular Simulations Inc., 9685 Scranton Road, San Diego, CA 92121-3752, USA

AM1 calculations are performed to study the non-linear optical properties of pushpull polyenes. On adopting dierent donor
and acceptor groups in hexatriene a set of hexatriene derivatives is obtained whose bond length alternations (BLA) are calculated
to be [0.070 to 0.110 , ranging from a charge-separated form to a neutral polyene form. Another parameter, d@ is also
DA
introduced to characterize the eectiveness of donoracceptor pairs. The relationships between the polarizabilities and d@ or
DA
BLA are investigated, giving an insight into the electronic origin of the linear and non-linear responses of these donoracceptor
substituted polyene molecules. The results may provide structural guides on selecting donor and acceptor groups for synthesizing
molecules with desired non-linear optical (NLO) properties.

1 Introduction
Conjugated organic molecules containing donor and acceptor
groups are known to exhibit large non-linear optical
responses due to the delocalization of the p electrons.1,2
Extensive research eorts have already been devoted to the
structureproperty relationships both in theory and in practice.3h14 One of the fundamental questions of interest is how
the polarizabilities of these molecules vary with the donor
acceptor combinations, the bridge and the medium. By focusing solely on the eect of donoracceptor substitutions, simple
polyene derivatives can be derived to provide a typical class of
organic NLO chromophores to carry out quantum mechanical calculations in order to gain an insight into the relationship between the molecular structures and NLO properties.
Semi-empirical calculations were often adopted for emphasis in interpreting the experimental trend.3,5h7,10,15,16 For
example, linear relationships between the calculated and
experimental NLO properties have been demonstrated via
PM-3/FF (nite eld) calculations,4d while AM1 calculations
are also widely utilized.12,13 Both of these methods can give
reliable results that are comparable to each other. To test this,
we have performed AM1 and PM3 calculations simultaneously on a few typical pushpull polyenes and compared
the results with experiments. For instance, the experimental k
(dipole moment) and b (rst-order hyperpolarizability) of
Et N(CHxCH) CHO are 6.5 D (1 D B 3.335 64 ] 10~3 C m)
2
2
and 20 ] 10~30 esu, while AM1 calculated values are 6.8 D
and 17.2 ] 10~30 esu, being comparable to the PM3 results
which are 5.2 D and 13.7 ] 10~30 esu, respectively. Therefore,
with the xed bridge studied here, we perform solely AM1
calculations on a series of donoracceptor substituted hexatrienes.
First, the strength of the substituted donoracceptor pair
that maintains the asymmetry of the electron charge distribution in the polyene molecule should be well characterized. As
we know, in a study of hyperpolarizabilty, such asymmetry in
simple p-organic systems is reasonably described by the algebraic sum of the Hammett constants for the substituted donor
and acceptor groups,17 i.e. ; p \ p
[p
.
p
p, acceptor
p, donor
However, if additional substituents are appended to the
chromophore this approach encounters some difficulties.
The S1 equivalents for the NLO polarizabilities used in this paper
are as follows : for k, 1 au \ 2.542 D \ 8478 ] 10~30 C m ; for a, 1
au \ 1.649 ] 10~41 C2 m2 J~1 ; for b, 1 au \ 3.206 ] 10~53 C3 m3
J~2 \ 8.641 ] 10~33 esu ; for c, 1 au \ 6.240 ] 10~71 C4 m4
J~3 \ 5.040 ] 10~40 esu.

Therefore, a more detailed investigation is needed.

In the Huckel molecular orbital treatment,3,11 the Coulomb
energy a is used to specify the orbital of an atom or a group
forming part of the p-bonded structure of the molecule, while
the dierence a [ a , referring to the coupling of the donor
A
D
and acceptor orbitals, characterizes qualitatively the donor
acceptor strength. That is, the smaller the value of a [ a ,
A
D
the larger the strength will be. On the other hand, according
to classical valence bond theory,18 the ground state chromogen can be regarded as a hybrid of two limiting resonance
forms, i.e. the neutral polyene structure and the chargeseparated (zwitterionic) structure where the degree of mixing
of the two limiting forms determines the BLA, the dierence
between the average lengths of the single and double carbon
carbon bonds in the polyene skeleton which is also related to
the donoracceptor strength. For the donoracceptor hexatrienes under consideration, BLA equals (b ] d)/
2 [ (a ] c ] e)/3 (see structure I).

Both a [ a and BLA have been adopted by Marder and

A
D
co-workers as parameters. They correlated the rst-order
hyperpolarizability b with parameter a [ a ,3,11 and they
A
D
also demonstrated that the polarizabilities a, b and c are all
well correlated to BLA.10,13c However, the translation of such
a trend to the corresponding real molecular structures is
worth exploring in detail, because in most cases, the value of
a [ a is unknown for a given substituted donoracceptor
A
D
pair,18 as is the correspondence between the BLA and the
substituted polyene.
Very recently, a two-band model was proposed by Suzuki et
al.20 to describe the NLO responses and the intramolecular
adiabatic charge-transfer mechanism of pushpull polyenes.
They derived a formula for the rst-order hyperpolarizability
b as a function of the localized energy level and the coupling
constants that characterize the end groups in pushpull
polyenes.
Here the model treatment is based on the ground-state
wavefunction-dening parameters d and d to characterize
D
A
the eectiveness of donor and acceptor, respectively. Here d
D
stands for the energy dierence between the HOMO (highest
occupied molecular orbital) of the donor-substituted polyene
and that of the unsubstituted polyene, namely E(HOMO)
D
J. Chem. Soc., Faraday T rans., 1998, 94(1), 4752

47

Published on 01 January 1998. Downloaded on 17/12/2014 03:47:10.

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[ E(HOMO) ; similarly, d is dened as E(LUMO)

P
A
A
[ E(LUMO) where E(LUMO) represents the lowest
P
A
unoccupied orbital energy of the acceptor-substituted polyene.
They dier from Suzukis parameters E , E which are shifted
d a
from the values calculated by the quantum mechanical
approach for the isolated molecules. Furthermore, we dene
d to be d [ d and will use it to represent the strength of
DA
D
A
donoracceptor pair.
By performing AM1 calculations on a series of donor,
acceptor and donoracceptor substituted hexatrienes, we
found monotonic trends exist among d , BLA and dipole
DA
moments, implying that the rst two can be equally well used
as parameters for characterizing the strength of donor
acceptor pairs and correlating the variation of polarizabilities
for pushpull polyenes. An explicit correspondence is gained
between molecular structures and NLO properties for substituted hexatrienes which would also be valuable for interpreting other polyenes or conjugated systems possessing
variable NLO responses.
In section 2, the methodology is outlined. In succession, we
discuss how to rationalize the eectiveness of individual donor
and acceptor groups appropriate for specifying donor
acceptor interaction in a wide range of d and BLA values.
DA
Then we introduce a set of pushpull hexatrienes with varying
donoracceptor strength. Each hexatriene derivative is subjected to a full geometry optimization with the AM1 method
and the corresponding values of BLA, the dipole moments
and the polarizabilities a, b, c are computed. In section 4, the
relationship between dierent structure parameters, d and
DA
BLA, is discussed. In section 5, we show how the plots of polarizabilties vs. d as well as BLA can be utilized for selecting
DA
donor and acceptor groups for synthesizing molecules with
desired non-linear optical responses. Lastly, the relations
among the polarizabilities of dierent orders is discussed.

2 Computational methodology
The non-linearity of the medium response with respect to an
external electric eld (F) is characterized by P, the induced
macroscopic polarization21
P \ D(1)F ] D(2)FF ] D(3)FFF ]

(1)

where D(n) (n \ 1, 2, . . .) stands for the nth order susceptibility

tensor of the bulk medium. Accordingly, p , the microscopic
i
polarization for an individual molecule can be expressed as
1
p \; K F ] ; Q F F
ijk j k
i
ij j 2
j
j, k
1
] ; E F F F ]
(2)
ijkl j k l
6
j, k, l
where the tensor components K , Q and E are the polariij ijk
ijkl
zability, rst-order and second-order hyperpolarizability
respectively, while F represents the electric eld component
i
along the ith axis (i \ x, y, z). For simplicity, the applied electric eld F is set to be uniform with zero frequency.
The calculations are implemented by using the MOPAC
system22 where the MNDO Hamiltonian is adopted with
AM1 parameterization, and the SCF convergence is set to
10~12. Tensor components, K , Q , and E of the molecules
ij ijk
ijkl
are computed for zero frequency in terms of the nite-eld
procedure combined with the energy-expansion method.23,24
The calculated tensors are then averaged according to the following equations :
K \ ; K /3
ii
i
3
Q \ ; Q k /pkp
i i
5
i
48

J. Chem. Soc., Faraday T rans., 1998, V ol. 94

4
; E /5
(3)
iijj
6
i, j
where k is the ith component of dipole moment, pkp is the
i
norm of the dipole moment and b is dened by
i
b \; b
(4)
i
ijj
j
E\

3 Donoracceptor pairs
In pushpull systems, the eectiveness of donor and acceptor
groups is crucial in understanding the structural changes and
relative properties.14 Both the electron-donating capacity and
electron-withdrawing ability of the typical substituted groups
have been currently arranged in descending sequence such as
NMe [ NHMe [ SMe [ NH [ SH [ OMe [ OH
2
2
for donor groups and

(I)

SO CF [ NO [ SO Me [ SOCF [ CN
2 3
2
2
3
[ COOH [ CONH [ CHO [ NO (II)
2
for acceptor groups available elsewhere.25
Upon adopting dierent combinations of these donor and
acceptor groups, various pushpull polyenes result. However,
in order to study the inuence of donoracceptor substitutions on the NLO behaviour over a wide range, it is suggested
that additional, stronger donoracceptor pairs should be
found. This can be achieved simply by substituting two donor
(acceptor) groups isolated or in joint form on the terminal
carbon atom of hexatriene. For example, two amino
radicals (H N)
and a propylidenediamino radical
2 2
HNCH CH CH NH are such donor groups, they are
2
2
2
stronger than a single amino group, while two CN radicals as
a whole withdraw electrons more efficiently than one cyano
group in the substituted polyenes. By such an extension more
donoracceptor combinations can be derived, providing a
large number of pushpull species for our investigation. Thus,
it is benecial to have some universal parameters to characterize the strength of donoracceptor pairs in these molecules.
First, it is necessary to scale the eectiveness of the donor
and acceptor groups. For this purpose, one should select the
model compound appropriately. By analogy with the establishment of the relationship between the Hammett free energy
and the electron-donating (or the electron-withdrawing) abilities of the conventional substituents from the experimental
measurements of ionization constants for the corresponding
substituted benzoic acids,17 in this work, we propose to use
one-sided donor-substituted hexatrienes and acceptorsubstituted hexatrienes as model compounds to characterize
the eectiveness of the conventional groups and the multiple
substituents. The eectiveness of all the employed donor and
acceptor groups can be compared in terms of parameters d
D
and d and the calculated values of the HOMO and LUMO
A
energies of the model compounds in reference to those of
unsubstituted hexatriene, respectively. For example, the dierence in HOMO energies between (H N) C(CH) CH and
2 2
4
2
hexatriene is employed to characterize the electron-donating
ability of (NH ) while the dierence in LUMO energies
22
between H C(CH) C(CN) and hexatriene is used to measure
2
4
2
the electron-withdrawing capacity of (CN) . In Table 1, nine
2
donor groups numbered from D to D with signicantly
1
9
separated d values are listed in descending donating ability.
D
Similarly, in Table 2, acceptor groups numbered from A to
1
A are selected and their d values tabulated. For complete13
A
ness, other groups in sequences (I) and (II) are also given in
Tables 1 and 2.
In comparison with the Huckel molecular orbital treatment,3 parameter d \ d [ d can play the role of a [ a
DA
D
A
A
D

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Table 1 Values of d , BLA and dipole moments of one-sided donorD

substituted hexatrienes (the hexatriene chains are in trans
conguration)

D
1
D
2
D
3
D
D4
5
D
6
D
7
D
D8
9

donor
group

model
compound

NH(CH ) NH
23
(NH )
22
O(CH ) NH
23
NH(CH )
Me N 2 4
2
H N
2
MeO
Me
H

D C(CH) CH
1
4
2
D C(CH) CH
2
4
2
D C(CH) CH
3
4
2
D C(CH) CH
4 CH
2
D4CH(CH)
5
4
2
D CH(CH) CH
6
4
2
D CH(CH) CH
7
4
2
D CH(CH) CH
4
2
H8C(CH) CH
2
4
2

d /eV
D

BLA/

k/D

1.26
1.05
1.01
0.97
0.91
0.81
0.45
0.19
0.00

0.084
0.086
0.092
0.093
0.098
0.097
0.102
0.107
0.110

3.8
2.1
3.7
2.3
2.1
2.2
2.0
0.4
0.0

Published on 01 January 1998. Downloaded on 17/12/2014 03:47:10.

Table 2 Values of d , BLA and dipole moments of one-sided

A
acceptor-substituted hexatrienes (the hexatriene chains are in trans
conguration)a

A
A1
2
A
A3
4
A
5
A
6
A
7
A
8
A
9
A
A10
A11
A12
13

acceptor
group

model
compound

(SO CF )
3 2 CF )
(NO2 )(SO
2
2 3
(SOCF )
3
2
(CN)(SO CF )
2 3
(NO )
22
SO CF
2 3
OC(NHCOw)
2
(CN)
2
NO
CHO
Br
F
H

H C(CH) CA
H2C(CH)4CA1
2
4 2
H C(CH) CA
2
H C(CH)4CA3
2
4 4
H C(CH) CA
2
4 5
H C(CH) CHA
2
4
6
H C(CH) CA
2
4 7
H C(CH) CA
2
4 8
H C(CH) CHA
2
4
9
H C(CH) CHA
H2C(CH)4CHA10
H2C(CH)4CHA11
H2C(CH)4CH 12
2
4
2

for characterizing the strength of substituted donoracceptor

pairs. It is instructive to place the zero point of d coincident
DA
with that of the BLA, an alternative parameter dened from
valence bond treatment.25 For this purpose, we set d \ 0 in
DA
case that the substituted polyene has, on average, equal single
and double bond lengths, i.e. the cyanine form chromophore is
dened by BLA \ 0. In other words, all d are numerically
DA
shifted to d@ \ d [ d
in our later discussions,
DA
DA
DA(cyanine)
where d
(characterizing the strength of donor
DA(cyanine)
acceptor pair of the substituted hexatriene in the cyanine
form) has been determined to be 3.51 eV. With this convention, the strength of a donoracceptor pair of substituted
hexatriene represented by d@ can be derived from Tables 1
DA
and 2, where the strongest pair symbolized by D [ A refers
1
1
to the largest value of d@ \ 0.95 eV, while the weakest one
DA
refers to the unsubstituted hexatriene with the lowest value of
d@ \ [3.51 eV (see Table 3). The former is expected to be in
DA
the zwitterionic form whereas the latter obviously exists in the
neutral form. Their BLA and dipole moments will be investigated in the following section.

d /eV
A

BLA/

k/D

4 Relationship between structure parameters

[3.20
[2.64
[2.35
[2.25
[2.13
[1.92
[1.56
[1.39
[1.04
[0.79
[0.39
[0.26
0.00

0.060
0.079
0.087
0.086
0.090
0.097
0.095
0.098
0.102
0.106
0.108
0.102
0.110

11.2
9.7
7.7
7.9
7.8
8.7
4.3
5.2
3.7
3.9
1.7
1.5
0.0

All the substituted hexatrienes derived from the donor and

acceptor groups cited in Tables 1 and 2 can be treated by
means of AM1 calculations via full geometry optimizations.
The BLA and dipole moment, which reect the resonance
structure and the polarity of the molecule, respectively, give
insights into the dependence of the structure variation and the
extent of charge separation on the strength of donoracceptor
pairs. We notice that the strength of donoracceptor pairs
controls both the BLA and the dipole moments for the substituted hexatrienes where a minor dierence of d@ induces
DA
approximately equal BLA (or dipole moments). Therefore, a
subset of them, say 30 species with donoracceptor strengths
spread uniformly over the interval from d@ \ [3.51 to 0.95
DA
eV are taken as representatives to examine the behavior of the
BLA, dipole moments and polarizabilities for donoracceptor
substituted hexatrienes.

a The calculated d (or d ), BLA and dipole moments for other substiD
A
tuted groups in sequences (I) and (II) are cited as follows : SMe \
2
0.88, 0.104, 1.5 ; SH \ 0.65, 0.105, 1.2 ; NO \ 1.34, 0.102, 6.3 ;
2 ; CN \ 0.75, 0.105,
SOCF \ 1.03, 0.105, 2.1 ; SOMe \ 1.08, 0.104, 5.9
3
3.5 ; COOH
\ 0.93, 0.106, 5.7 ; CONH \ 0.58, 0.109, 4.4.
2

Table 3 d@ , BLA, dipole moments (k), polarizabilities (a) and hyperpolarizabilities (b, c) of donoracceptor substituted hexatrienes
DA
no.

donor

acceptor

d@ /eV
DA

BLA/

k/D

a/10~23 esu

b/10~30 esu

c/10~36 esu

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

A
A1
A2
A3
A4
A5
A6
A7
A10
A1
A2
A5
A8
A1
A5
A1
A2
A6
A8
A1
A5
A6
A8
A7
A8
A9
A10
A9
A12
A11
13

0.95
0.39
0.10
0.00
[0.12
[0.33
[0.69
[1.46
0.74
0.18
[0.33
[1.07
0.70
[0.37
0.66
0.10
[0.62
[1.15
0.60
[0.47
[0.68
[1.21
[1.14
[1.67
[2.02
[2.27
[2.28
[3.06
[2.93
[3.51

[0.070
[0.025
[0.008
[0.001
0.020
0.031
0.042
0.073
[0.061
[0.016
0.032
0.061
[0.044
0.039
[0.036
0.012
0.053
0.069
[0.020
0.054
0.063
0.076
0.067
0.087
0.092
0.096
0.098
0.099
0.105
0.110

26.9
22.9
19.4
20.3
17.0
17.2
11.6
8.5
24.5
20.7
14.4
9.2
24.8
15.4
23.5
18.7
14.6
9.2
21.8
13.2
13.8
8.7
8.5
7.4
5.5
5.9
4.3
1.8
2.1
0.0

6.26
6.88
7.45
6.86
6.41
6.16
6.77
4.75
5.33
5.69
5.03
4.50
6.63
6.02
6.92
7.04
5.89
5.38
6.64
5.44
5.27
4.75
4.93
3.98
3.45
3.38
3.11
2.56
2.83
2.01

[64.99
[44.42
[23.08
[10.78
36.72
37.86
58.49
33.91
[51.72
[22.37
37.38
35.32
[60.61
46.90
[50.70
18.96
50.26
43.00
[25.44
62.53
54.36
43.09
41.91
20.36
20.49
14.44
14.10
0.68
1.35
0.00

83.69
[136.18
[147.71
[163.00
[86.34
[24.77
55.22
109.44
31.82
[115.49
[11.79
77.63
[15.52
8.25
[54.53
[141.49
64.94
116.54
[103.60
90.34
99.07
122.65
84.56
75.18
69.66
62.17
52.35
26.98
33.24
13.38

D
D

3
4

D
D6
7
D
D

8
9

J. Chem. Soc., Faraday T rans., 1998, V ol. 94

49

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These thirty representative compounds are displayed in

Table 3 with the donoracceptor pairs symbolized by D (n \
n
1, 2, . . . , 9) and A (m \ 1, 2, . . . , 13) numbering from 130. In
m
terms of the descending order for the donor eectiveness, they
are classied into nine sets, and members within each set are
arranged in decreasing order of acceptor eectiveness. For
instance, species 18 contain a common donor group D , (the
1
propylenediamino group), but dierent acceptor groups from
A to A of decreasing electron-withdrawing ability.
1
10
The calculated BLA and dipole moments together with d@
DA
for these thirty species are collected Table 3. (BLA and dipole
moments for one-sided substituted hexatrienes are tabulated
in Tables 1 and 2). They show monotonic variation trends
consistent with the decreasing order of acceptor eectiveness
within each set of substituted hexatrienes. An overall consistent relationship among BLA, dipole moments and d@ for all
DA
the thirty substituted hexatrienes is also shown diagramatically in Fig. 1 (a) and (b). The smoothness of all plots
indicates that each of these three quantities can be used as a
parameter for rationalizing the donoracceptor strengths of
the substituted hexatrienes.
In terms of BLA, substituted hexatrienes are currently typied in reference to three extremes, i.e. BLA @ 0, BLA \ 0 and
BLA A 0 which correspond to zwitterionic, cyanine and
neutral resonance forms, respectively.14 The same classication can be used in terms of d@ with respect to the
DA
extremes of d@ A 0, d@ \ 0 and d@ @ 0, which correspond
DA
DA
DA
to strong, medium and weak donoracceptor pairs, respectively. From Table 3, it is anticipated that species denoted 1, 9
and 13 with formulae (CH ) (NH) C(CH) C(SO CF ) ,
23
2
4
2 32
(NH ) C(CH) C(SO CF )
and
(CH ) (NH)C(CH) C
22
4
2 32
24
4
(SO CF ) , will be almost in the zwitterionic form, because
2 32
their BLAs are equal to [0.070, [0.061 and [0.044 and
d@ of the donoracceptor pairs takes the values of 0.95, 0.74
DA
and 0.70 eV, respectively. On the other hand, the
unsubstituted hexatriene (30 in Table 3), which has the largest
BLA and the least negative d@ , refers to the neutral resoDA

Fig. 1 The relationship between parameter BLA and d@ (a) and

DA
that between dipole moment and d@ (b) for the 30 donoracceptor
DA
substituted hexatrienes

50

J. Chem. Soc., Faraday T rans., 1998, V ol. 94

nance form, while species 3 and 4, with a common donor 1,5propylidenediamino (D ), but dierent acceptor groups
1
(SO CF ) and (CN)(SO CF ) of approximately the strength,
2 32
2 32
exist in the cyanine form due to their BLA or d@ approaching
DA
zero. Dipole moments are also consistent with the extent of
charge separation, which varies from 0 (neutral) through 20.3
(cyanine) up to 26.4 D (zwitterionic) for these 30 species.

5 Molecular polarizabilities
So far, we have focused attention on the strength of donor
acceptor pairs which is crucial in studying the behaviour of
pushpull polyenes. In comparison with BLA, d@ is another
DA
useful parameter for characterizing the behaviour of donor
acceptor pairs but one with the advantage that it can be
obtained from some model compounds rather than the substituted species itself and that the one-to-one correspondence
between the parameter and the donoracceptor pair is
explicit. Based on these structureproperty relationships the
behaviour of the linear and non-linear optical responses in a
series of pushpull species for a given bridge, can be better
investigated and interpreted.
Following the methodology described in section 2, we have
calculated the molecular polarizabilities a, b and c for zero
frequency for all the thirty molecules tabulated in Table 3.
These polarizabilities are plotted vs. d@ and BLA, respecDA
tively, in Fig. 2.
The diagrams in Fig. 2 provide information about how the
polarizabilities change with the donoracceptor pair strength.
Molecules with d@ B 0 eV (or BLA B 0 , k B 20.0 D)
DA
exhibit large a, zero b and negative c (minimum). This corresponds to the occurrence of the cyanine resonance form with
delocalization and uniform distribution of p electrons. Around
the interval of d@ from about [1.6 to [0.4 eV (or BLA
DA
about 0.040.08 , k about 147 D), the molecules are expected to be composed of more of the neutral form than of
the zwitterionic form, and possess large rst-order (b) and
second-order (c) NLO susceptibilities. While d@ [ 0 (or
DA
BLA \ 0), the substituted hexatrienes will be almost in the
zwitterionic form of high polarity, resulting in negative b and
the appearance of another positive peak for c. These results
are in qualitative agreement with the previous theoretical and
experimental results.3,10h14 However, in our calculations, we
use a series of donoracceptor pairs instead of the action of a
variable applied eld on a denite molecule, such as 9(dimethylamino)nona-2,4,6,8-tetraenal,10 to induce and to
compare the variation of the linear and NLO properties
because the latter approach may overestimate the eects in
comparison with that produced by real donoracceptor pairs
or solvents.16
From the thorough treatment of substituted hexatrienes,
three typical patterns can be classied below. One might ask
which category is the most suitable to provide candidates for
large NLO responses. Based on the above discussions along
with Tables 13, we can draw the following preliminarily conclusions :
(1) For one-sided donor- (acceptor-) substituted hexatrienes,
we have d \ 0 (d \ 0), so d@ \ d [ d
and d@ \
A
D
DA
D
DA(cyanine)
DA
[d [ d
for donor- and acceptor-substituted hexaA
DA(cyanine)
trienes, respectively. Both the calculated values of d@ and
DA
BLA are distant from the peak points of the b- and c-curves
(see Fig. 2), which means that only a minor NLO enhancement will occur in these molecules.
(2) For hexatrienes substituted by single donor and single
acceptor groups, d@ (or BLA) can take values from [3.51 eV
DA
(or 0.11 ) to [0.68 eV (or 0.063 ), which are fairly close to
the peak point d@ \ [0.47 eV (or BLA \ 0.05 ) with a conDA
siderable positive b on the curve, indicating that single donor
acceptor substitution can reasonably improve the rst-order
hyperpolarizability. However, the value of c in this case can
reach a positive peak at d@ \ [1.2 eV (or BLA \ 0.075 )
DA

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Fig. 2 Plots of (a) *k/*d@ , (b) *a/d*@ , (c) *b/*d@ and (d) *c/*d@ ( ) and AM1 calculated a, b, c () with tted curves () vs. d@ and
DA
DA
DA
DA
DA
BLA

when some donoracceptor combinations, for example, the

NH and SO CF are selected as substituted groups.
2
2 3
(3) It is of interest to note in our results that b is signicantly enhanced by introducing an additional donor and/or
acceptor substitutuent at the termini of the hexatriene chain.
Ratner and co-workers15 have demonstrated that multiple
donoracceptor substitution increases b negligibly as in the
dimethylamino-nitro substituted hexatriene. The value of d@
DA
(or BLA) is equal to [0.3 eV (or 0.03 ), on the left (or right)
side of the peak value of d@ \ [0.47 eV (or BLA \ 0.05 )
DA
with an insignicant b, implying that this donoracceptor pair
is too strong. Table 3 reveals that some multiple donor
acceptor substitutions can aect d@ (or BLA) signicantly, so
DA
one can obtain substituted hexatrienes with large rst- or
second-order hyperpolarizabilities by selecting adaptive combinations of multiple donor and/or multiple acceptor groups
(refer to Tables 13). For example, the value of d@ is equal to
DA
[0.47 eV for the substituted hexatriene of the D A pair
5 5
which is predicted to be an efficient NLO molecule with

b \ 62.5 ] 10~30 esu, while substituted hexatrienes with

D A and D A pairs are expected to be candidates with
1 10
5 8
large c values.

6 Relation among polarizability of dierent orders

The dipole moment for a molecule in a perturbing eld F is
equal to the sum of the permanent dipole moment k and the
0
microscopic polarization p expressed by eqn. (2) which is also
i
known as the induced dipole moment. It reveals that the static
polarizabilities at a given value of F are equal to the partial
derivatives of the dipole moment with respect to F in stepwise
increasing order as follows
a(F) \ [dk(F)/dF]

,
F?0
b(F) \ [d2k(F)/dF2]
\ [da(F)/dF]
,
F?0
F?0
c(F) \ [d3k(F)/dF3]
\ [db(F)/dF]
,
F?0
F?0
d(F) \ [d4k(F)/dF4]
\ [dc(F)/dF]
F?0
F?0
J. Chem. Soc., Faraday T rans., 1998, V ol. 94

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51

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These relations were illustrated by Marder and co-workers

in terms of INDO calculations on (CH ) N(CHxCH) CHO
32
4
in the presence of an external electric eld F determining the
optimized values of parameter BOA (p-bond order
alternation).13 Because BOA is a function of F, plots of k, a, b
and c vs. BOA predicted directly from INDO calculations and
those of numerically dierentiated k, a, b and c with respect to
F vs. BOA could be compared. Qualitatively good consistency
has been shown among these two kinds of curves, allowing
prediction of higher polarizability as a function of BOA.
In the present work, AM1 calculations on a set of real molecules presents curves of dipole moments, polarizabilities a, b
and c plotted vs. d@ and BLA in Fig. 1 and 2. By the same
DA
principle, curves for polarizabilities a, b and c can be derived
by performing numerical dierentiations of k, a, b and c with
respect to d@ (or BLA), respectively, assuming the eective
DA
eld strength is linearly dependent on the donoracceptor
strength, i.e., F \ a ] d with a \ 0.48. The results are disDA
played in Fig. 2 by dashed lines and the predicted curve of d
(the third-order hyperpolarizability) is also given in Fig. 2(d).
The similarity between the curves for a, b and c of dierent
origin in Fig. 2 is obvious, in particular, the peaks and valleys
are almost coincident. It reveals that the results of our
numeric experiment on real molecules seem to demonstrate
the derivative relationships in fact hold reasonably well over a
wide range of d@ or BLA.
DA

2
3
4

5
6
7
8
9
10
11
12
13

14

7 Conclusions
Semi-empirical AM1 calculations are performed for a set of
pushpull hexatrienes with donoracceptor pairs of varying
strength. The relationship between calculated polarizabilities
and BLA is found to be in good agreement with previous
results. d@ is suggested as another parameter to represent the
DA
strength of a donoracceptor pair which can be obtained from
some model compounds rather than the pushpull hexatrienes
themselves. The plots of polarizabilities vs. d@ could be valuDA
able for selecting donor and acceptor groups for synthesizing
molecules with predictable non-linear optical responses. Our
calculations have been conned to isolated molecules (gas
phase). It is assumed that the qualitative relationships between
d@ (or BLA) and polarizabilities, which are obtained in this
DA
work (see Fig. 2), are also applicable to molecules in the condensed phase. The role of the polar medium is to induce a
decrease in d@ (or BLA). In other words, if experimental or
DA
theoretical studies provide us with the value of d@ or BLA for
DA
a molecule in the condensed phase, we can estimate its hyperpolarizability directly from the curves in Fig. 2. Further study
including the eect of solvents is now under progress.
We greatly appreciate the referees comments and suggestions.
This work was supported by China NSF.

15
16
17
18
19
20
21
22
23
24
25

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J. Chem. Soc., Faraday T rans., 1998, V ol. 94

Paper 7/03928J ; Received 5th June, 1997