PHYSICAL REVIEW B 74, 205435 2006

Frequency-dependent nonlinear optical properties of CdSe clusters

Sabyasachi Sen and Swapan Chakrabarti*
Department of Chemistry, University of Calcutta, 92-A. P. C. Ray Road, Kolkata-700 009, India
Received 7 June 2006; revised manuscript received 27 September 2006; published 29 November 2006
Nonlinear optical properties of CdSe clusters have been investigated using time dependent density functional
theory. Finite and negative values of static and frequency dependent first order hyperpolarizability have been
observed in case of CdSe and Cd3Se3 while the same is absent in Cd2Se2 and Cd4Se4. At specific frequencies,
sudden increase in the frequency dependent components of first order hyperpolarizability tensor second
harmonic generation has been attributed to the near resonance of the input energy. Three components of
second order hyperpolarizability tensor have been calculated by combining analytical and finite difference
techniques. The results indicate that these clusters have a high degree of nonlinear optical properties.
DOI: 10.1103/PhysRevB.74.205435

PACS numbers: 42.65.k, 36.40.c, 31.15.Ew

I. INTRODUCTION

In recent years nonlinear optical NLO materials have

created substantial research interest due to their application
in high-speed electro-optic EO devices for information processing and telecommunications.14 These materials also find
tremendous applications in optical switching and optoelectronics. Various experimental as well as theoretical results
have established the importance of small metallic clusters as
potential candidates for NLO material.5,6 An example of such
a class of materials having manifestation of unusual physicochemical and optical properties is cadmium selenide clusters CdnSen and quantum dots.710
The response of the materials to the application of static
or time varying electric field is the key ingredient in the
design and investigation of NLO materials. Response properties of molecular system in general involves energy derivatives namely polarizabilities and hyperpolarizabilities. The
electric dipole moment can be expanded into different orders
of external fields. It is represented as

a = aEb = Ec = Ed . . = 0 + abEb
b

+ 1/2 ! abcEbEc + 1/3 ! abcdEbEcEd ,

bc

bcd

where Ear , t , Ebr , t , . . ., are the external electric fields consisting of a monochromatic and a static part and the Cartesian directions a , b , . . . equal to x, y, or z. In the expansion,
the first term corresponds to permanent dipole moment of the
sample. ab, abc, and abcd represent the elements of linear
polarizability tensor, first order hyperpolarizability tensor
and second order hyperpolarizability tensor, respectively.
Time dependence of dipole moment leads to various frequency dependent polarizability and hyperpolarizability tensors. The first order hyperpolarizability tensor is described in
terms of three frequency dependent components namely second harmonic generation SHG 2 ; , , electrooptical Pockels effect EOPE ; , 0, optical rectification OR 0 ; , and the static first order
hyperpolarizability 0 ; 0 , 0. In the same way, in addition
to the static analog 0 ; 0 , 0 , 0 the frequency dependent
components of second order hyperpolarizability tensor are
1098-0121/2006/7420/2054356

third harmonic generation THG 3 ; , , , electrooptical Kerr effect EOKE ; , 0 , 0, dc-induced second harmonic generation dc-SHG 2 ; , , 0 and intensity dependent refractive index IDRI ; , ,
or degenerate four-wave mixing DFWM. Among NLO
properties, the first order hyperpolarizability takes a prominent place, as it is the simple third order molecular property
and responsible for phenomena such as SHG and EOPE.11
The second order hyperpolarizability is optically significant
as the sign of it is rudimentary in molecular design
procedure.12 Second order hyperpolarizability and its enhancement due to physical transformations e.g., change in
size has been studied extensively in earlier studies.13 Further
it involves physical properties such as EOKE.
A large number of theoretical as well as experimental investigations have already demonstrated NLO properties of
cluster materials.14,15 NLO processes provide significant information for proper understanding of quantum confinement
and surface effects in clusters. Presence of NLO properties in
metallic clusters Al4M4 has been demonstrated numerically
by Datta et al.6 In the present work the focus is on a semiconducting cluster namely CdnSen. Hyper Rayleigh scattering technique provides the experimental basis of NLO properties in CdSe clusters and nanoparticles.14 Aktsipetrov et al.
has shown size dependence of SHG from the surface of a
composite material consisting of CdSe nanoparticles embedded in a glass matrix.16 The first order hyperpolarizability in
CdSe and CdS nanoparticles is reported to be very high.14,17
Emerging interests in ab initio methods and development
of computational techniques provide strong impetus for exploring NLO properties of CdnSen at the numerical level.
Recently Karamanis et al.18 have used DFT for the computation of static polarizability and anisotropy in static polarizability of CdSe clusters but the frequency dependent optical
properties have not been addressed in their work. Moreover
the numerical justification of the observed hyperpolarizabilities in CdnSen was also not their point of discussion. In the
present work we investigate the frequency dependent NLO
properties of CdnSen using time dependent density functional
theory TDDFT as our prime investigating tool.19 Within
TDDFT both the local density approximation LDA and
generalized gradient approximation GGA technique have

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PHYSICAL REVIEW B 74, 205435 2006

SABYASACHI SEN AND SWAPAN CHAKRABARTI

been used. More accurate LB94 van Leeuwen and Baerends

9420 functional has been used under GGA scheme
A. Computational details

Geometries of CdSe, Cd2Se2, Cd3Se3, and Cd4Se4 have

been optimized separately for triplet and singlet states using
B3LYP21,22 type exchange-correlation functional and 3
-21G* basis set. The geometry optimizations are implemented in Gaussian 03 program.23 Triplet and singlet geometries are optimized using spin polarized and nonpolarized
spin restricted calculations, respectively. Results obtained
reveal that for the clusters under investigation, singlet state
optimized geometries are more stable than those of the triplet
state counterparts. Hence spin restricted calculations are performed during the evaluation of response properties. The singlet state optimized geometries are consistent with the DFT
calculation of Karamanis et al.18 Response calculations have
been implemented in the Amsterdam density functional
package ADF 2004.01.24 The density functional technique
used here involves spin restricted calculations under both
generalized gradient approximation GGA and local density
approximation LDA. The exchange-correlation functional
of Vosko-Wilk and Nusair VWN Ref. 25 is used in the
LDA scheme. The GGA counter part of exchange correlation
potential is that of van Leeuwen and Baerends LB94.20 The
use of LB94 removes the discrepancies occurring in
asymptotic region. The basis set chosen is TZP, which consists of a triple zeta basis augmented with a polarization
function. Analytical approach has been used for the evaluation of response properties in ADF. Average values of polarizability, anisotropy in polarizability, static hyperpolarizability, second harmonic generation SHG, electro-optical
Pockels effect EOPE, and optical rectification OR are obtained at the output of the response program.
II. RESULTS AND DISCUSSIONS

Singlet state optimized geometries of CdSe, Cd2Se2,

Cd3Se3, and Cd4Se4 are presented in Fig. 1. The data obtained is in corroboration with the theoretical prediction of
Karamanis et al.18 Similar results were also obtained in earlier DFT calculation of Deglmann et al.26 In their work DFT
potential surface investigations were performed for small
CdSe clusters, up to heptamer.
The response calculation can be performed in two different techniques. The first of the two is the finite difference
technique and the other one is the analytical approach. In
finite difference technique, energy is calculated for different
values of electric field; thereafter finite differentiation is performed to attain the derivative of energies. The viability of
the method depends on the choice of the strength of perturbation. Although this method is suitable for any program
capable of energy calculation in a perturbed system, its main
deficiency is a prolonged computational time. The problem
becomes more severe if the calculation involves higher order
derivatives of the energy. On the contrary, inside analytical
approach desired properties are obtained from a single calculation, i.e., by evaluating the derivatives of the energy ana-

FIG. 1. Color online Singlet state optimized geometries of

CdSe, Cd2Se2 , Cd3Se3, and Cd4Se4; the footnote of each structure
contains the ground state energies in a.u.

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FREQUENCY-DEPENDENT NONLINEAR OPTICAL

TABLE I. Average static first and second order hyperpolarizability in CdSe, Cd2Se2 , Cd3Se3, and Cd4Se4.
Sample

Average static first order

hyperpolarizability
a.u.

Average static second order

hyperpolarizability
a.u.

CdSe
Cd2Se2

540.07 LDA
Absent

Cd3Se3

0.12258 LDA
0.059125 LB94
Absent

556680 LDA
7306.5 LDA
4398.6 LB94
12200 LDA
8929.3 LB94
89565 LDA
50124 LB94

Cd4Se4

lytically. Consequently, an analytical approach is often preferred in a response calculation. Van Gisbergen et al.19 have
successfully applied this technique for a comparative study
of frequency dependent hyperpolarizabilites of a set of small
molecules. In their work, data obtained with various exchange correlation potential was compared with different ab
initio methods to show the capability of the analytical approach. The premier advantage of this approach is that it
gives access to frequency dependent properties and the data
obtained are more accurate.
Frequency dependent polarizability and hyperpolarizability tensors are obtained from the trace of the dipole moment
matrix Ha and the nth order density matrix Dn where
n = 1 for the linear polarizability , n = 2 for first order hyperpolarizability tensor , and n = 3 for second order hyperpolarizability , and so on. If the inducing electric field of
frequency b, c. . . acts in the direction a, b, c. . . the tensors
can be represented as

FIG. 3. Color online Variation of 2 ; , and

; , 0 with frequency at LDA scheme.

where = b + c + . These expressions are a set of generalized equations in terms of frequencies. Polarizability and

hyperpolarizability tensors defined above, are determined

through the iterative solution of time dependent Kohn-Sham
TDKS equations. In the calculation initially static KohnSham KS equation is solved whose results are used to arrive at the solution of first order KS equations. The solution
of first order KS equation results in frequency dependent
polarizability ab ; b. The solution of first order
equation provides the ingredients for an iterative solution of
the second order equations. The technique adopted is called
2n + 1 theorem. The solution of second order equation provides second order density matrix elements from which frequency dependent first order hyperpolarizability tensor is obtained. If external fields of frequency 0 and some common
frequency are considered, a number of very important
NLO properties become accessible. These are SHG
2 ; , , EOPE ; , 0, OR 0 ; , , and
the static hyperpolarizability 0 ; 0 , 0. Similar to previous
two cases, 2n + 1 theorem is also used to compute the
higher order hyperpolarizability tensors such as , , third
order hyperpolarizability tensor and the rest. When is
calculated only at frequencies 0 and , THG
3 ; , , ,
EOKE
; , 0 , 0,
dc-SHG
2 ; , , 0, IDRI ; , , become accessible.

FIG. 2. Color online Variation of 2 ; , and

; , 0 with frequency at LDA scheme.

FIG. 4. Color online Variation of 2 ; , and

; , 0 with frequency at GGA LB94 scheme.

ab ; b = TrHaDbb,
abc ; b, c = TrHaDbcb, c,
abcd ; b, c, d = TrHaDbcdb, c, d,

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FIG. 5. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at LDA scheme.

FIG. 7. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at GGA LB94 scheme.

Earlier studies have already demonstrated the suitability

of DFT for computing linear polarizability and
hyperpolarizabilities.27,28 The calculated polarizability and
hyperpolarizabilities depend on the choice of basis set and
exchange-correlation potential. While the results obtained
within DFT are overestimated under normal LDA and GGA
functional, coupled Hartree-Fock procedure exhibits exactly
the opposite trend.29,30
The first order hyperpolarizability tensor is defined as the
third derivative of the energy with respect to the electric field
components and hence involves one additional field differentiation compared to polarizabilities. The average first order
hyperpolarizability is defined as

duced appreciably 0.122 58 a.u. for Cd3Se3 and absent in

Cd2Se2. In the case of Cd4Se4, the nonvanishing tensor components are xyz, yxz, xzy, zxy, yzx, zyx. Because of the
above definition, vanishes in this case.
Second order hyperpolarizability tensor involves one additional field differentiation compared to the first order analog. The average second order hyperpolarizability is defined
as

* 1/2
,
i i

i = 1/3 ijj + jij + jji,

j

where the sums are over the coordinates x, y, z i, j = x, y, z

and *i refers to the conjugate of the vector i. Table I depicts
the static values of average first order hyperpolarizability
0 ; 0 , 0 and average second order hyperpolarizability
0 ; 0 , 0 , 0 of CdSe, Cd2Se2, Cd3Se3, and Cd4Se4 and it
indicates 0 ; 0 , 0 is higher 540.07 a.u. for CdSe, re-

FIG. 6. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at LDA scheme.

= 1/15 2iijj + ijji,

i, j = x,y,z.

ij

In the present investigation components of second order hyperpolarizability tensors are determined from a combination
of analytical and finite difference techniques.19 All components of the tensor of interest dc-SHG/EOKE/static second order hyperpolarizability can be obtained from analytical time-dependent calculation of SHG/EOPE/static first
order hyperpolarizability in the presence of small electric
fields. For example the relation used in the evaluation of
EOKE is

abcd ; ,0,0 = lim abc ; ,0E=Ed/Ed .

Ed0

FIG. 8. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at LDA scheme.

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FIG. 9. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at GGA LB94 scheme.

The frequency dependence of 2 ; , , ; , 0,

2 ; , , 0, ; , 0 , 0, is thoroughly investigated.
For a complete evaluation of NLO properties in different
CdSe clusters a wide range of frequencies 0 a.u. to
0.45 a.u. have been considered. Figures 24 manifest the
frequency behavior of 2 ; , and ; , 0 for
CdSe and Cd3Se3, respectively. 2 ; , being a frequency dependent property is of a paramount interest and has
been investigated extensively in previous works.11,14,31 High
degree of fluctuations in 2 ; , are observed for
both the cases. Experimentally, 2 ; , in CdSe nanocrystals and quantum dots has been observed by HRS technique and its size dependence was also verified.14 It is evident from Figs. 24 that 2 ; , and ; , 0
exhibit negative values over a wide range of frequencies.
When the LDA results compared to that of LB94, the magnitude of both 2 ; , and ; , 0 are significantly suppressed for Cd3Se3. The variation of
; , 0 in LB94 scheme is similar to that of LDA
results. Moreover the high negative maxima of
2 ; , as observed in LDA is absent in LB94. LB94
fails to produce response properties of CdSe as it has nearly
degenerate HOMO-LUMO level. It is legitimate to mention
that normal LDA and GGA functional generally provide too
large values if compared with the experimental or accurate
correlated wave function data.29,30 The frequency variation in
2 ; , divulge one more significant information i.e.,
the abrupt increase in 2 ; , at specific frequencies.
At specific frequencies the magnitude of 2 ; , becomes very high. It is a common notion that larger values of
2 ; , are obtained at near resonance of the input
energy.5 The presence of near resonance indicates linear absorption can occur at such frequencies. Therefore we conjecture that at input photon energies below 0.22 a.u., frequency
dependent first order hyperpolarizability calculation on CdSe
can be performed without any hindrance. In case of Cd3Se3
the same is 0.360 a.u.
Contributions from second order hyperpolarizability,
2 ; , , 0 and ; , 0 , 0 have been plotted in
Figs. 511. Similar to 2 ; , and ; , 0 the

FIG. 10. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at LDA scheme.

components of second order hyperpolarizability tensors

2 ; , , 0 and ; , 0 , 0 are highly sensitive
to frequency variation. It is quite obvious from both LDA
and LB94 results that both 2 ; , , 0 and
; , 0 , 0 are negative over a wide range of frequencies. The frequency dependence of the hyperpolarizability
components becomes more interesting when a comparison is
made with their static counterparts. In the case of CdSe,
2 ; , , 0 is highly negative over a wide range of
frequencies compared to the static analog 0 ; 0 , 0 , 0.
Similarly, ; , 0 , 0 shows high negative values over a
number of frequencies. For the clusters Cd2Se2, Cd3Se3, and
Cd4Se4 with positive 0 ; 0 , 0 , 0, the frequency dependent counterparts exhibit negative values at different
frequencies. The occurrence of negative values of
2 ; , , 0 and ; , 0 , 0 is also the case with
LB94.
The nature of variation in 2 ; , , 0 is fairly identical in all four samples. Moreover, LB94 results also exhibit
same variations. This observation is supported by Figs. 611.
It is also noticeable that in spite of the slight disagreement
occurring in the case of Cd3Se3, the frequency dependence of

FIG. 11. Color online Variation of 2 ; , , 0 and

; , 0 , 0 with frequency at GGA LB94 scheme.

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SABYASACHI SEN AND SWAPAN CHAKRABARTI

; , 0 , 0 as observed in LDA is well in agreement

with its GGA LB94 counter part Figs. 611. Thus the
presence of static hyperpolarizabilities and also their frequency dependent counterparts establish the numerical justification of NLO properties in CdSe, Cd2Se2, Cd3Se3, and
Cd4Se4.
III. CONCLUSIONS

In the present investigation we have demonstrated the numerical evidence of NLO properties in CdSe, Cd2Se2,
Cd3Se3, and Cd4Se4. Both LDA and GGA LB94 functionals have been used in the study. The simulated results predict
that the average static first order hyperpolarizability in CdSe
and Cd3Se3 are finite and negative while the same is absent
in Cd2Se2 and Cd4Se4. In frequency variation of
2 ; , , the abrupt increase at specific frequencies is
interpreted as near resonance of input energies. A combina-

*Corresponding author. Email address: swapanchem@yahoo.co.in

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tion of analytical and finite difference techniques provide

2 ; , , 0, ; , 0 , 0, and 0 ; 0 , 0 , 0. It is
worth mentioning that the present investigation deals only
with small CdSe clusters and hence is very difficult to predict the possible nature of scaling of both static and frequency dependent dynamic hyperpolarizabilities. However,
the work of Karamanis et al.18 illustrates that average static
polarizability converges to that of the bulk material for
Cd4Se4. The possible nature of scaling of static and dynamic
hyperpolarizabilities will be considered in our future work
on large CdSe clusters.
ACKNOWLEDGMENTS

We acknowledge the financial support from the UGC,

Govt. of India Xth plan to purchase the ADF program. The
authors wish to convey their special thanks to George Maroulis, University of Patras, Greece, for his valuable suggestions.

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