JOURNAL OF CHEMICAL PHYSICS VOLUME 118, NUMBER 5 1 FEBRUARY 2003

Mechanism of linear and nonlinear optical effects of KDP and urea crystals
Zheshuai Lin, Zhizhong Wang, and Chungtian Chen
Technical Institute of Physics and Chemistry, Beijing Center for Crystal Research and Development,
Chinese Academy of Sciences, P.O. Box 2711, Beijing, 10080, People’s Republic of China
Ming-Hsien Lee
Department of Physics, Tamkang University, Tamsui, Taipei 251, Taiwan
共Received 16 July 2002; accepted 6 November 2002兲
First-principles calculations of the linear and nonlinear optical properties of KH2PO4 共KDP兲 and
CO共NH2) 2 are presented. The calculations are an extension of methods we developed earlier and
applied to borate crystals. Electronic band structure obtained from a pseudopotential method is input
to the calculation. For two crystals considered, the resulting indices of refraction, birefringence, and
nonlinear optical coefficients are in good agreement with experiments. The origin of nonlinear
effects has been explained through real-space atom-cutting analysis. For KDP, the contributions of
PO4 groups to second-harmonic generation effect are dominant, and the hydrogen bonds contribute
much more to birefringence. For both KDP and urea, the contributions from the virtual electron
process to nonlinear optical responses are dominant. © 2003 American Institute of Physics.
关DOI: 10.1063/1.1533734兴

I. INTRODUCTION tion, Zhang et al.7 reported an ab initio study of the

electronic and structural properties of the ferroelectric tran-
The very first materials to be used and exploited for their sition in KDP. To our knowledge no first-principle calcula-
nonlinear optical 共NLO兲 and electro-optic 共EO兲 properties tion of nonlinear optical coefficient of KDP has appeared in
were potassium dihydrogen phosphate 共KDP兲 and ammo- literature.
nium dihydrogen phosphate 共ADP兲. They were used in the As discussed in the review of Halbout and Tang,8 crys-
early experiments in nonlinear optics and they are still talline urea was among the first organic materials to find an
widely used in nonlinear optical devices. They also continue application in nonlinear optics, specifically phase-matched
to be popular as electro-optic materials because they are
second-harmonic generation 共SHG兲 in the ultraviolet region.
readily grown in useful sizes with good optical homogeneity.
From a fundamental point of view, this crystal is interesting
The nonlinear coefficients of other nonlinear optical crystals
because it is among the simplest organic crystals that have
show considerable variation from crystal to crystal, which is
second-harmonic responses. The unit cell of urea crystal with
not the case for the KDP group, there is better agreement
among the reported values for their nonlinear coefficients P4̄21m space group symmetry is shown in Fig. 1共b兲. Urea is
than for other materials. The electro-optic and nonlinear op- also hydrogen bonded, which leads to enough delocalization,
tical properties of KDP and its isomorphs were reviewed by yet it has strong localized features such as ␲ electrons in the
Eimerl.1 The crystal structure of KDP belongs to the acentric carbonyl groups which contribute significantly to nonlinear
orthorhombic point group mm2 in its ferroelectric phase be- response. Levine and Allan have reported a first-principles
low 123 K, and above this temperature belongs to the acen- calculation for the urea crystal and pointed out that nonlinear
tric tetragonal point group 4̄2m in the paraelectric phase.2 local-field corrections are important.9 Earlier, Morrell and
The unit cell of KDP having I4̄2d space group3 is shown in co-workers performed a complete neglect of differential
Fig. 1共a兲. In the KDP structure, fundamental PO4 units are overlap/spectroscopic 共CNDO/S兲 calculation on urea
bonded together through the H atoms in the hydroxy groups crystal.10 An earlier complete neglect of differential overlap
of the O’s of PO4. The structure of KDP is not complicated, 共CNDO兲 method is also used to calculate the dielectric
however, the spontaneous polarization in the material does constant.11
not provide a complete description of acentricity. Levine has In recent years, we have reviewed the calculation
applied the bond charge model calculations to arbitrary space methods of the second-harmonic generation 共SHG兲 based on
group, and in particular to KDP.4 Reasonable agreement with first principles and suggested an improved calculation
experimental data was obtained with extrapolation of empiri- formula.12,13 The calculation requires input describing the
cally determined effective parameters. A few studies of ab electronic band structure, which we obtained from CASTEP,14
initio calculations for KDP have been published. In 1992 a total energy calculation computer software package. We
Hao et al.5 calculated and discussed the potential energy sur- have used our method to successfully calculate linear and
face for the O–H¯O bond in KDP. In 1993 Silvi and his nonlinear optical 共NLO兲 responses of a series of important
colleagues investigated the electronic structure and the pro- NLO crystals such as BBO,13 LBO, CBO and CLBO,15
ton transfer potential energy curve by a periodic Hartree– BIBO,16 KBBF,17 NaNO2, 18 and SrBe3O4. 19 The origins of
Fock quantum chemical method.6 In a very recent publica- the SHG effects of these crystals were clearly explained

0021-9606/2003/118(5)/2349/8/$20.00 2349 © 2003 American Institute of Physics

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2350 J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Lin et al.

trons in which the effects of the free charge carries can be

neglected, the nonlinear optical properties of a materials are
mainly determined by the magnitudes of the static limit of
the SHG coefficients ␹ (2) (0), which plays the most impor-
tant role in the applications of SHG crystals. We adopt the
representation of the second-order susceptibility
␹ ␣␤␥ ⫽ ␥ ␣␤␥ 共 VE兲 ⫹ ␹ ␣␤␥ 共 VH兲 ⫹ ␹ ␣␤␥ 共 two bands兲 , 共1兲
where ␹ ␣␤␥ (VE) and ␹ ␣␤␥ (VH) denote the contributions
from virtual-electron processes and virtual-hole processes,
respectively, and ␹ ␣␤␥ (two bands) gives the contribution
from two band 共TB兲 processes to ␹ (2) . The formulas for
calculating ␹ ␣␤␥ (VE), ␹ ␣␤␥ (VH), and ␹ ␣␤␥ (two bands)
are as follows:

␹ ␣␥␥ 共 VE兲 ⫽
e3
兺
2ប 2 m 3 v cc ⬘
冕 d 3k
4␲3
␤
P 共 ␣␤␥ 兲 Im关 p ␣v c p cc ⬘ p c ⬘ v 兴
␥

⫻ 冉 1
2 ⫹
␻ 3c v ␻ v ⬘ c
2
␻ 4v c ␻ c ⬘ v
冊 , 共2兲

兺 冕
e3 d 3k ␣ ␤
␹ ␣␥␥ 共 VH兲 ⫽ P 共 ␣␤␥ 兲 Im关 p vv ⬘ p v ⬘ c p ␥c v 兴
2ប 2 m 3 vv ⬘ c 4␲3

⫻ 冉 1
2 ⫹
␻ 3c v ␻ v ⬘ c
2
␻ 4v c ␻ c v ⬘
冊 , 共3兲

and

␹ ␣␥␥ 共 two bands兲 ⫽

e3
ប 2m 3
兺
vc
冕 d 3k
4␲3
P 共 ␣␤␥ 兲

Im关 p ␣v c p ␤c v 共 p ␥vv ⫺ p cc
␥
兲兴
⫻ . 共4兲
FIG. 1. Unit cell of KDP and urea crystals. 共a兲 KDP, 共b兲 urea. ␻ 5v c
Here, ␣, ␤, and ␥ are Cartesian components, v and v ⬘ denote
valence bands, and c and c ⬘ denote conduction bands.
by using atom-cutting analysis method. This analysis method P( ␣␤␥ ) denotes full permutation. The band energy differ-
isolates the contribution of individual atoms or groups of ence and momentum matrix elements are denoted as ប ␻ i j
atoms by removing spatial localized wave functions from the and p ␣i j , respectively.
evaluation.
The structural parameters of KDP crystal with I4̄2d
The goal of this work is to calculate the electronic struc-
space group symmetry are taken from the work of West3 and
tures and the linear and nonlinear optical parameters of KDP
are a⫽b⫽7.43 Å and c⫽6.97 Å. In a primitive cell there
and urea crystals from first-principles quantum mechanics
are four KDP molecules. Crystalline urea belongs to P4̄21m
and to give an explanation of the origin of the optical re-
space group. Its geometry is taken from the work of Guth
sponses. Results of the calculations on KDP and urea crystals
et al.24 and are a⫽b⫽5.572 Å and c⫽4.686 Å. In a primi-
show that our calculation method is adequate for KDP and
tive unit cell there are two urea molecules.
urea crystals.

III. RESULTS AND DISCUSSIONS

II. COMPUTATIONAL METHOD
In the following we separately give the calculated results
The plane-wave pseudopotential total energy software and discussions for KDP and urea crystals.
package CASTEP14 is used for solving the electronic and band
structure. These results are applied to the calculations of lin- A. KDP
ear and nonlinear optical properties of the crystals. The the-
oretical basis of CASTEP is the density functional theory 1. Energy bands of KDP
共DFT兲.20 The optimized pseudopotentials in the Kleinman– The calculated energy bands along the line of high sym-
Bylander form for C, N, O, P, K, and H21–23 allow us to use metry points in the Brillouin zone are illustrated in Fig. 2.
a small plane-wave basis set without compromising the ac- The total density of states 共DOS兲 and partial DOS 共PDOS兲
curacy required by our study. For systems with bond elec- projected on the constitutional atoms are plotted in Fig. 3.

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J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Optical effects in KDP and urea crystals 2351

below ⫺15 eV. It is composed of the O 2p and the P 3s

orbital with a little mixing H 1s. The middle subregion is the
valence band which is very flat. The VB is mostly from the
O 2p and the P 3p with small contribution from H and K
orbitals. The K-p-derived state is located about ⫺10 eV. The
upper subregion is the conduction band which consist mainly
of the O 2p and the P 3p with small contribution from H and
K orbitals.

2. Linear optical response of KDP

It is known that the refractive indices can be obtained
theoretically from the dielectric function. The imaginary part
of the dielectric function can be calculated with the matrix
elements which describe the electronic transitions between
the ground state and the excited states in the crystal consid-
ered. The formula is given by

冕
i j
e2 f nm p nm p mn
Im[ 共 ⑀ i j 共 ␻ 兲兴 ⫽
␲ m 2ប
兺
mn
dk
␻ nm
2
␦ 共 ␻ nm ⫺ ␻ 兲 ,
共6兲

where f nm ⫽ f n ⫺ f m , and f n , f m are Fermi factors. The real

part of the dielectric function is obtained by the Kramers–
Kronig transform.28
In Table I we listed theoretical refractive indices and
birefringence of KDP. The calculated refractive indices of
KDP are in good agreement with experimental values. The
calculated birefringence ⌬n⫽0.042 is in reasonable agree-
ment with the measured value ⌬n⫽0.035.
To investigate the respective contributions of different
ionic groups, we employed the real-space atom-cutting
method.13 With this method the contribution of ion A to the
FIG. 2. Band structure of KDP crystal. nth-order susceptibility, denoted as ␹ (n) (A), is obtained by
cutting all ions except A from original wave functions, i.e.,
␹ (n) (A)⫽ ␹ All
(n)
ions except A are cut . In a previous paper we
found that the charge density around the cation is spherical.13
Both the top of the valence band 共VB兲 and the bottom of the
Thus we first choose the cutting radius of K as 1.40 Å. Fol-
conduction band 共CB兲 are at G 共gamma point兲. The direct
lowing the rule of keeping the cutting spheres of the cation
band gap of 4.178 eV is obtained, which is significantly
and O in contact and not overlapped, we choose the cutting
smaller than the experimental value of 7.12 eV 共⬃174 nm兲.25
radii of O and P atoms to be 1.10 and 1.25 Å, respectively.
The calculated band gaps are usually smaller than the corre-
The atom-cutting analysis results are also given in Table I.
sponding experimental ones with density functional theory.
The contributions to refractive indices of the PO4 group
To fit the measured absorption edge, the energy scissors op-
dominate, but birefringence contribution of the PO4 group,
erator is commonly employed to shift up all conduction
having symmetrical tetrahedral structure, is only 0.0247. In
bands.26,27 For the calculation of KDP the scissors energy
the BPO4 calculation 共theoretical ⌬n⫽0.005) we also found
3.00 eV was applied. Assuming that the rmn matrix elements
that the symmetrical tetrahedral structures have small contri-
are unchanged, the momentum matrix elements should be
bution to birefringence. Furthermore we calculated the con-
renormalized regarding the change of the Hamiltonian in a
tribution to birefringence of the H2PO4 group and obtained
way given by
⌬n⫽0.0495. This shows that hydrogen bond contribution to
birefringence is almost double that of the PO4 group. The
␻ nm ⫹⌬/ប 共 ␦ nc ⫺ ␦ mc 兲 result of atom-cutting analysis indicates that K⫹ has almost
p nm →p nm , 共5兲
␻ nm nothing to do with the birefringence. This result is in accor-
dance with our previous conclusions for LBO, CBO, CLBO,
where the subscript c in Kroneckers represents conduction and other materials.15–17
band, and the ⌬ factor restricts the correction to pairs of band
only involving one valence-band and one conduction-band 3. The nonlinear optical response of KDP
state. It is known that the second order susceptibility ␹ (2) is a
From Figs. 2 and 3 it can be seen that the band structure double of the SHG coefficient d i j . According to the Kleim-
is separated into three subregions. The lower one is located man symmetry relation29–31 there is only a single indepen-

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2352 J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Lin et al.

FIG. 3. DOS and PDOS plot of KDP

crystal.

dent SHG coefficient d 14⫽d 36 for KDP with 4̄2m point cutting method applied to the calculation of the SHG coeffi-
group symmetry. The calculated nonlinear coefficient of cients are also given in Table I. Comparison of d 36(H2PO4)
KDP crystal is 0.42 pm/V which is in good agreement with and d 36(PO4) shows that hydrogen bond has small contribu-
the experimental value of 0.39 pm/V.25 Results of the atom- tions to the SHG effect. Apparently, the anionic groups

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J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Optical effects in KDP and urea crystals 2353

TABLE I. Comparison of the calculated and experimental values of refrac- TABLE II. The contributions of SHG coefficients of different transitions for
tive indices, birefringence and SHG coefficient, together with atom-cutting KDP and urea 共unit: pm/V兲.
analysis results for KDP crystal.
Crystals KDP Urea
nx ny nz ⌬n d 36 共pm/V兲
d 36 共Calc.兲 0.42 1.043
Expt.a 1.495 35 1.495 35 1.460 41 0.035 0.39 Contributions
Calc. 1.5518 1.5518 1.5104 0.0415 0.42 VE 0.406 1.083
Atom-cutting analysis VH 0.010 ⫺0.04
PO4 1.4649 1.4649 1.4402 0.0247 0.417 TB 0.000 0.00
H2PO4 1.4977 1.4977 1.4482 0.0495 0.421
K 1.1125 1.1125 1.1112 0.0013 0.004

the other hand, the contribution from the virtual hole 共VH兲
a
Reference 25.
process to the SHG effect are 2.4% and 3.8% for KDP and
urea, respectively.
(PO4) ⫺3 contribute approximately 99% to SHG coefficients,
and cation K⫹ has nothing to do with the SHG effect.
B. Urea crystal
To investigate the respective influence of the various
transitions on the optical responses of the KDP and urea 1. Energy bands of urea
crystals, the contributions of different transitions to SHG ef- The calculated energy bands along lines of high symme-
fect are calculated. The results are given in Table II. The try and the total density of the states 共DOS兲 of crystalline
contribution from the virtual electron 共VE兲 process to the urea are given in Fig. 4. The partial DOS projected on the
SHG effect closely approaches the experimental value. On constitutional atoms is shown in Fig. 5. Both the top of the

FIG. 4. Band structure and DOS plot

of urea. k points are the same as that in
Fig. 2.

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2354 J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Lin et al.

FIG. 5. PDOS plot of urea crystal.

VB and the bottom of the CB are at point G 共gamma point兲. come from 2p orbitals of C, O, and N. The upper subregion
The direct band gap of 4.27 eV has been obtained. This value is the conduction band 共CB兲, which shows the apparent in-
is smaller than the experimental value of 6.18 eV 共⬃200 teraction between C and N valence orbitals. These interac-
nm兲. The scissors energy 1.91 eV was used to fit the mea- tions between orbitals of C, N, and O 共bonding兲 reveal that
sured values. The energy bands are flat and not seriously the framework OCN2 in urea molecule is an entity.
dispersive. This is a typical characteristic of small intermo-
lecular interactions for molecular crystals. Both energy band
and DOS figures show the entire energy bands are divided 2. Linear optical response of urea
into three subregions. The lowest subregion is below ⫺15 eV For urea crystal the calculated refractive indices and bi-
and is composed of three isolate sharp spike peaks. The peak refringence are listed and compare with experimental values
centered at ⫺20 eV is the mixture of C, N, and O 2s orbitals. in Table III. The theoretical values are in good agreement
The other two peaks are composed of C and N 2s orbitals. with the experimental data. Both theoretical and experimen-
The middle subregions are valence bands 共VB兲 from 0 to tal birefringence values are ⌬n⫽0.1.
⫺9.0 eV and consist of two parts. The top of the VB consists The calculated charge density contour is shown in Fig. 6.
of C and O 2p orbitals. The peaks from ⫺4 to ⫺9 eV mostly This charge density map indicates that the CO共NH2) 2 is an

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J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Optical effects in KDP and urea crystals 2355

TABLE III. Calculated and experimental refractive indices, birefringence TABLE IV. Comparison of experimental and calculated SHG coefficients of
and atom-cutting analysis results for urea crystal. urea from this work and others.

␭ 共nm兲 nx ny nz ⌬n ␭ 共nm兲 d 14 共pm/V兲

a
Expt. 1064 1.4720 1.4720 1.5817 0.1132 CNDO 1064 0.89
Calc. 1064 1.5037 1.5037 1.6247 0.1210 LDA 共no local field兲b ⬁ 2.1
Contributions of transition between VB and CB bands of respective LDAb ⬁ 1.1
groups Present work ⬁ 1.044
VB CB Expt. crystalc 1060 1.2⫾0.1
CO CO 1.3463 1.3463 1.4615 0.1152 Expt. crystald 600 1.3⫾0.3
CO NH2 1.2670 1.2670 1.2981 0.0311
a
NH2 NH2 1.3974 1.3974 1.4269 0.0322 Reference 11.
b
NH2 CO 1.3028 1.3028 1.3328 0.0300 Reference 6.
c
Reference 32.
d
Reference 30.

entity. That is to say, we cannot cut any cation or anion from

the molecule, so we should treat it as a whole. The contribu- ment between the theoretical and experimental values is
tions of different types of electron transitions are given in good. For comparison in Table IV we have listed other the-
Table III. Apparently, all transitions contribute to the linear oretical investigations of the SHG coefficients of crystalline
optical response, but the birefringence of urea crystal origi- urea. The theoretical value of semiempirical CNDO calcula-
nates mainly from the transitions between VB and CB of the tion does not agree as well with the experimental one be-
conjugated group CO. The other transitions in urea crystal cause the intermolecular interaction was not included.11
contribute little to the anisotropy. Levine and Allan9 reported the LDA calculation results with-
out and with the local field, and the latter was found in good
agreement with the experimental measurements. Present re-
3. The nonlinear optical response of urea
sults are consistent with the Levine and Allen calculation that
Levine and Allan have pointed out that for the case of included the local field.
urea, it is necessary to invoke Kreinman symmetry,29–31 To investigate the respective influence of the various
which is appropriate far from resonance. Urea crystal be- transitions on the optical responses of the urea crystal, the
longs to point group 4̄2m. There are two possible SHG co- contributions of different transitions to SHG effect were cal-
efficients for this point group, and Kreinman symmetry re- culated. The results are given in Table II. We found the con-
quires d 123⫽d 312 . In compressed notation this is d 14⫽d 36 . tribution from the virtual electron process to the SHG effect
The SHG coefficients have been also calculated from the closely approaches the experimental value. On the other
band energies and wave functions using the computational hand, the contribution from the virtual hole process to the
formulas 共1兲–共4兲. The calculated SHG coefficients at the SHG effect is only ⫺0.04 pm/V, but its sign is opposite to
static limit d 14⫽1.04 pm/V are given in Table IV. The agree- that of the virtual electron process. In our previous investi-

FIG. 6. Charge density contour plot on the CO共NH2 ) 2 plane of urea crystal.

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2356 J. Chem. Phys., Vol. 118, No. 5, 1 February 2003 Lin et al.

gation on the mechanism for linear and nonlinear optical real-space atom-cutting method can reveal the origins of the
effects of ␤-BaB2O4 共BBO兲 crystal, we have pointed out that optical responses for NLO crystals. We believe that further
generally the virtual electron process contributes more to the applications of the methodology used in present work may
total response than the virtual hole process.13 However, in elucidate the origins of the optical effects, both linear and
the case of BBO crystal the contribution to the large compo- nonlinear, in other NLO crystals and help us to find and
nent d 22 from virtual hole process is about 30% of the total design new NLO crystals more efficiently.
nonlinear optical response. This is unlike the case of GaAs
for which the contribution of the VH process is always nega- ACKNOWLEDGMENTS
tive and is smaller than that of the VE process by over an
order of magnitude. This difference is based on the different This work was supported by the Chinese National Key
structures of the energy bands of zinc-blende semiconductors Research Project. Support in computing facilities from the
and borate crystals. The energy gaps of semiconductors are Computer Network Information Center is gratefully ac-
much smaller than those of the borate crystals. The organic knowledged. M.H.L. thanks funding support from NSC 90-
urea crystal is different from both the zinc-blende semicon- 2102-M-032-011.
ductors and borates. For urea crystal the top of the VB is
very flat and the band gap is large. The dominant contribu- 1
D. Eimerl, Ferroelectrics 72, 95 共1987兲.
tion to the SHG value is given by the VE process. In addition 2
S. H. Wemple and M. DiDomenico, Jr., Appl. Solid State Sci. 3, 263
the transitions related to the CO group contribute more than 共1972兲.
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J. West, Z. Kristallogr. 74, 306 共1930兲.
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B. F. Levine, Phys. Rev. B 7, 2600 共1973兲.
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23
M.-H. Lee, J.-S. Lin, M. C. Payne, V. Heine, V. Milman, and S. Crampin
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24
H. Guth, G. Heger, S. Klein, W. Treutmann, and C. Scheringer, Acta
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V. G. Dimitriev, G. G. Gurzaddyan, and D. N. Nikogosyan, Handbook of
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26
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J. E. Sipe and E. Ghahramani, Phys. Rev. B 48, 11705 共1993兲.
Above-mentioned conclusions confirm that the CASTEP 29
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30
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K. Betzler, H. Hesse, and P. Loose, J. Mol. Struct. 47, 393 共1978兲.
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J.-M. Halbout, S. Blit, W. Donaldson, and C. L. Tang, IEEE J. Quantum
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