Ab initio Molecular Orbital Theory Study

of GaAs Clusters: The Geometry

PRAKASHAN P. KORAMBATH, BABU B. K. SINGARAJU,
SHASHI P. KARNA
Air Force Research Laboratory, 3550 Aberdeen Avenue, Bldg. 914, Kirtland AFB,
New Mexico 87117-5776
Received 19 May 1999; accepted 24 September 1999

ABSTRACT: We have studied the structure and geometry of neutral and charged
atomic clusters consisting of Ga and As atoms via ab initio HartreeFock (HF) and
second-order MllerPlesset methods. The Gam Asn cluster with m 6= n composition
prefers a nontetrahedral geometry in the charge neutral (q = 0) state. These clusters tend to
be stable in tetrahedral geometry when appropriately charged. The Gam Asn cluster with
m = n composition (1:1 ratio of Ga to As atoms) tends to be stable in a tetrahedral
geometry in the charge neutral (q = 0) state. With increasing size of the cluster, the
geometry of Gan Asn cluster approaches the zinc-belende-type crystalline structure.
c 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 563573, 2000

Key words: GaAs clusters; structure and stability; charge trapping

Introduction

alliumarsenide (GaAs) is a technologically

important material having applications in
electronics and optoelectronics devices [1]. Because
of these applications, the magnetic, electrical, optical, and optoelectronic properties of GaAs have
been the subject of extensive experimental and theoretical studies [2, 3]. A persistent, fundamental
problem, often limiting the device application of
GaAs, has been the presence of point defects. The
Ga and the As atoms have very similar electronegativity. Therefore, during epitaxial growth, the Ga
Correspondence to: P. P. Korambath.
Contract grant sponsor: National Research Council.

International Journal of Quantum Chemistry, Vol. 77, 563573 (2000)

c 2000 John Wiley & Sons, Inc.

atoms can easily replace As atoms and vice versa

without significantly changing the chemical environment of the material. However, such substitutions significantly alter the electronic environment
and electrical characteristics of the material. Similarly, vacancies and vacancy-antisite pairs created
in the materials during processing as well as upon
exposure to high-energy radiation affect the reliability and performance of GaAs-based devices [4, 5].
Therefore, in the past two decades, there have been
numerous experimental [6, 7] and theoretical studies [8] dedicated to characterizing and understanding the microscopic nature of point defects in GaAs.
Most of the current understanding about the nature of defects in GaAs is based upon electron spin
resonance (ESR) measurements. Unfortunately, due
to the higher value of the nuclear spin quantum

KORAMBATH, SINGARAJU, AND KARNA

number of Ga (I = 32 ) and As (I = 32 ) atoms,
the details of the ESR spectrum that provide the
information about the microscopic structure surrounding the paramagnetic nuclei are often lost and
complicated by the presence of many overlapping
components [6, 7].
It is possible to extract useful information from
ESR data with the help of quantum mechanical
calculations, and some attempts have been made
in this direction in the past [9, 10]. However, theoretical approaches used in these calculations [9,
10] place serious limitation on the reliability of the
results. More sophisticated calculations on point defects in GaAs have been mainly performed on the
energy minimization of local atomic structure models within the periodic potential approach [8]. While
such approaches are reasonable for calculating band
energy and also super-cell cluster stability, they do
not describe the localized properties such as the spin
distribution and hyperfine interaction. In view of
the importance of point defects in GaAs and a lack
of reliable data concerning their nature and properties, detailed study of these defects via ab initio
quantum mechanical methods is deemed highly desirable and timely.
Recent ab initio studies of point defects in
Si-based materials have shown that the details
of the microscopic properties of point defects in
solids can be reliably determined from calculations
using a cluster approach [11]. However, a potential
difficulty in studying point defects in GaAs using
an atomic cluster approach is the ability to generate
realistic model structures. A realistic model of
GaAs in the cluster approach must accurately
represent the local symmetry and the structure of
the crystal. GaAs forms a zinc-blende-type crystal
with face-centered-cubic (fcc) structure in which
each Ga atom is tetrahedrally bonded to four As
atoms and vice versa [2, 12]. When constructing
atomic clusters of GaAs with a minimal number
of atoms, the stable structures do not often retain
a tetrahedral (Td ) symmetry. As will be discussed
here, preserving a Td symmetry of a GaAs cluster
depends upon the number of binary atoms as well
as the total charge on the clusters. The latter condition is intimately related to the former. Therefore,
as a first step we have investigated the stability and
structural properties of finite size clusters consisting
of Ga and As atoms. For small clusters, the effects of
basis set and electron correlation on the geometry
have also been investigated.

564

VALENCY AND BONDING CONSIDERATIONS

Before proceeding to build molecular clusters
and optimize geometry, it is useful to discuss the valency and the nature of chemical bonds around Ga
and As atoms. Ga has three valence electrons with
the electronic configuration given by (core) 4s2 4p1 .
Arsenic has five valence electrons with its electronic
configuration given by (core) 4s2 4p3 . The core in
both cases consists of the inner-shell (n = 1, 2, 3)
electrons. Therefore, for Ga atom to form four tetrahedral (sp3 ) bonds, an extra electron needs to be
added to its valence shell. Similarly for the As atom
to form four tetrahedral (sp3 ) bonds, an electron
needs to be removed from its valence shell. For a
tetrahedral cluster Gan Asn consisting of an equal
number of Ga and As atoms, the extra electron required by the former is supplied by the latter, and
there is no need of extrinsic charge to be added or removed. However, for a cluster like Gam Asn (m 6= n)
with unequal number of Ga and As atoms, electrons
need to be added (m > n) or removed (m < n)
to obtain a tetrahedral geometry. This simple valency consideration allows one to successively build
tetrahedral atomic clusters consisting of Ga and As
atoms.
The smallest prototypical structures providing
the basis for building tetrahedral GaAs structures,
as shown in Figure 1, are (i) AB4 and (ii) B3 ABA3 ,
where A, B = Ga, As. Starting from either of the
two prototypical structures, (i) or (ii), one can successively build larger clusters of GaAs. However, it
is immediately clear that structure (i) has an unequal
number of Ga and As atoms. Therefore, as discussed
above, it would be charged in a tetrahedral geometry. Structure (ii), on the other hand, maintains the
1:1 ratio of Ga to As and does not require external
charges in order to be in stable tetrahedral geometry. While structure (ii) would not require external charges to maintain four-coordinated geometry,
some comments on the nature of the covalent bond-

FIGURE 1. (a) Model AB4 structure [structure (i)].

(b) Model B3 ABA3 structure [structure (ii)].

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GaAs CLUSTERS: THE GEOMETRY

ing between Ga and As atoms still seem to be in
order. The Ga atom, having only three valence electrons, contributes 0.75e to each of its four tetrahedral
bonds. The As atom, with its five valence electrons,
will contribute 1.25e to each of the four tetrahedral
bonds. Therefore, in the ideal condition, a GaAs
bond in structure (ii) tetrahedral cluster is not fully
covalent but has partial ionic character represented
by Ga As+ .

COMPUTATIONAL METHODS AND BASIS SETS

Calculations were performed using ab initio
HartreeFock (HF) and second-order MllerPlesset
(MP2) theory with the help of the GAMESS [13]
quantum chemistry package. Three different basis
sets were used in the calculations. These were: (i) a
relativistic compact effective potential (RCEP) [14],
also known as effective core potential (ECP); (ii) a
double-zeta polarization (DZP) (DZV + 3d functions
on heavy atoms and 1p function on light H atoms)
[15]; and (iii) a polarized even-tempered Gaussian
(ETG) basis set [16]. The exponents and contraction
coefficients of the ECP and the DZP basis sets are
available in the literature [14, 15]. The orbital exponents and the contraction coefficients of the ETG
basis set taken from Ref. [16] for Ga and As are listed
in Table I.

Model Structures
Guided by the above considerations, we started
with the two prototypical structures. (i) The first
set consisting of a central Ga/As atom coordinated
to four H atoms (Figs. 2 and 3) is of the type AB4
[Fig. 1(a)]. The larger clusters, GaAs4 H3+
12 and
were
built
from
the
(Ga/As)H
structure
AsGa4 H3
12
4
by replacing the H atoms with As/Ga atoms and
terminating the outer valency with H atoms. These
structures are shown in Figures 4 and 5. (ii) The
smallest cluster for the second prototypical-type
structure B3 ABA3 [Fig. 1(b)] is H3 GaAsH3 (Fig. 6).
The next larger cluster was built by replacing the H
atoms in Figure 6 with appropriate heavy (Ga/As)
atoms. The resulting structure H9 As3 GaAsGa3 H9
is shown in Figure 7. Additionally, a cluster with
composition (H2 GaAsH2 )3 was also constructed
(Fig. 8) to study a ring (closed) structure.

Results
THE AB4 SYSTEMS
+
The GaH4 , GaH
4 , AsH4 , AsH4

These molecules belong to the prototype cluster

structure AB4 [Fig. 1(a)]. We calculated the geometry of tetrahydrides of Ga and As. The optimized
structures of the neutral and negatively charged

TABLE I
Extended even-tempered Gaussian (ETG) basis set for Ga and As.a
Ga
Exponent

s Coef.

516560.650
172186.880
57395.628
19131.876
6377.292
2125.764
708.588
236.196
78.732
26.244
8.748
2.916
0.972
0.324
0.108

0.000148
0.000304
0.001508
0.005631
0.021830
0.079839
0.249136
0.501562
0.287720
0.419702
0.630390
0.646384
0.402947
1.000000
1.000000

a Contraction

p Coef.

0.000456
0.002245
0.015583
0.083890
0.352162
0.675742
1.000000
0.754289
0.315092
0.186478
0.860889

As
d Coef.

0.043105
0.233898
0.827793
0.609428
0.505871

s Coef.

p Coef.

0.000174
0.000353
0.001768
0.006536
0.025463
0.091494
0.279083
0.510399
0.234260
0.550925
0.501311
0.790018
0.247189
1.000000
1.000000

0.000547
0.002653
0.018437
0.096571
0.385246
0.636163
1.000000
0.842206
0.209815
0.561924
0.523260

d Coef.

0.049464
0.258969
0.805843
0.720476
0.383392

scheme = s (9, 2, 2, 1, 1); p (6, 1, 2, 2); d (3, 2).

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KORAMBATH, SINGARAJU, AND KARNA

(a)
(a)

(b)

(b)
FIGURE 2. (a) GaH4 molecule with three H atoms and

FIGURE 3. (a) AsH4 molecule with three H atoms and

a Ga atom in a plane and the fourth H atom in a

perpendicular plane. The parameters are optimized
using DZP basis set. (b) GaH
4 molecule in Td geometry.
The parameters are optimized using DZP basis set.

an As atom in a plane and the fourth H atom in a

perpendicular plane. The parameters are optimized
using DZP basis set. (b) AsH+
4 molecule in Td geometry.
The parameters are optimized using DZP basis set.

clusters of GaH4 using the DZP basis set are shown

in Figure 2. The optimized structures of neutral
and positively charged AsH4 using the DZP basis
set are shown in Figure 3. It is apparent that neutral tetrahydrides of Ga and As atoms do not have
a stable tetrahedral structure. The corresponding
charged clusters, on the other hand, are stable in
tetrahedral geometry. The neutral GaH4 has a pyra-

midal structure with three H atoms in a plane containing the Ga atom. The fourth H atom is located
perpendicularly above the GaH3 plane at distance
twice the other GaH distance. In this case the
fourth GaH bond represents an antibonding-type
orbital. The neutral AsH4 cluster also has a triangular pyramidal equilibrium structure with three
AsH bonds in a plane with the As atom and the

TABLE II
Ab initio HF and MP2 geometry optimization for
a
GaH
4 molecule.

TABLE III

Basis set

Re ()

Angle (deg)

Basis set

Re ()

Angle (deg)

ECP
ECP + PF on Ga
ECP + PF on Ga and H
ECP + PF on Ga + 6-31 on H
ECP + PF on Ga; MP2
ECP + PF on Ga and H; MP2
DZP
DZP; MP2

1.641
1.642
1.634
1.635
1.645
1.628
1.632
1.625

109.48
109.49
109.49
109.49
109.49
109.49
109.47
109.47

ECP
ECP + PF on As
ECP + PF on As and H
ECP + PF on As + 6-31 on H
ECP + PF on As; MP2
ECP + PF on As and H; MP2
DZP
DZP; MP2

1.481
1.491
1.480
1.480
1.509
1.485
1.474
1.477

109.48
109.47
109.48
109.47
109.48
109.48
109.48
109.48

aR

566

for X3 6 state of GaH = 1.663 [17].

a
Ab initio geometry optimization for AsH+
4 molecule.

aR

for X3 6 state of AsH is 1.5344 [17].

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GaAs CLUSTERS: THE GEOMETRY

FIGURE 4. GaAs4 H3+

12 molecule in Td geometry. The
parameters are optimized using DZP basis set.

fourth H atom in a perpendicular plane. However,

the bond distance is 0.72 shorter than that of the
other three AsH atom distances. An ECP basis
set calculation on neutral AsH4 cluster resulted in a
trigonal pyramidal structure with three H atoms at
1.519 pointing to the corners of the base triangle
and the fourth atom at the apex of the pyramid at
4.647 .
Optimized geometrical parameters for GaH
4 and
AsH+
4 obtained from the use of additional basis sets
and different theoretical methods are given in Tables II and III, respectively. Also listed in the tables
are the observed bond distances of X3 6 state of the
diatomic species Ga/AsH [17]. It is obvious from
the tables that regardless of the quality of the basis
set and the sophistication of the theoretical method
used in the calculations, the optimized equilibrium
geometry of the two charged clusters has a tetrahedral symmetry. For GaH
4 cluster, the changes in the
bond angles and bond distances due to the basis sets
are marginal. Inclusion of electron correlation (EC)
via MP2 with the ECP basis set reduces the GaH
bond length by about 0.013 but leaves the HGaH
angle basically unchanged. On the other hand, inclusion of EC via MP2 with the DZP basis set
reduces the bond distance only by 0.007 but leaves
the angles unchanged. The best calculated GaH
bond distance (DZP; MP2) is about 0.038 shorter

FIGURE 5. AsGa4 H3
12 molecule in Td geometry. The
parameters are optimized using DZP basis set.

than the corresponding experimental value for the

diatomic GaH species (Table II) in its X3 6 state.
A somewhat similar effect is noted on the geometry of AsH+
4 cluster due to basis sets. The ECP basis
set augmented with polarization functions (PF) on
the As alone gives an AsH bond length that is
slightly larger by 0.01 than those with PF on both
heavy as well as the light atoms. The all-electron
DZP basis set gives an AsH bond distance that
is too small by about 0.007 compared to that obtained with the ECP basis set. The effect of EC on the
geometry of AsH+
4 is different from that noted in the
+
case of GaH
4 . In the case of AsH4 , the EC effect with
the DZP basis set increases the AsH bond distance
by about 0.003 , and for the ECP basis set with PF
on As and H, the AsH bond length increases by
0.005 . However, the bond angles, similar to that
in the case of GaH
4 , seem to be rather insensitive
to the choice of the basis set and EC. Also, as noted
from Table III, the best calculated bond distance in
the case of AsH+
4 cluster obtained (DZP; MP2) is
about 0.05 shorter than the corresponding value
for the diatomic AsH species in its X3 6 state.
3
GaAs4 H3+
12 and AsGa4 H12

The next set of clusters were built by replacing

H atoms of Ga/AsH4 with Ga/As and terminat-

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KORAMBATH, SINGARAJU, AND KARNA

TABLE IV

Ab initio HF geometry optimization for GaAs4 H3+

12 molecule.
Bond distances ()
Basis set
ECP
DZP
ETG

GaAs

AsH

2.551, 2.558
2.553
2.618, 2.619

1.490, 1.489
1.481
1.517, 1.516

ing the valency of the outer atoms with H atoms

as shown in Figures 4 and 5. In their charge neutral
state (q = 0), the two clusters did not converge to
a stable geometry. In order to check the stability of
the charged clusters, we performed geometry optimization with charges q = 1, 2, and 3 for GaAs4 H12
and charges q = 1, 2, and -3 for AsGa4 H12 cluster. The only clusters exhibiting stable geometry
3
were the GaAs4 H3+
12 and AsGa4 H12 species. Both
these clusters exhibit tetrahedral symmetry around
the central heavy atom. The optimized GaAs4 H3+
12
and AsGa4 H3
12 clusters using the DZP basis set are
shown in Figures 4 and 5, respectively. The optimized bond distances and bond angles using three
3
different basis sets for GaAs4 H3+
12 and AsGa4 H12 are
given in Tables IV and V, respectively. For the Asrich cluster, the GaAs bond distance varies from a
low of 2.551 in the case of the ECP basis to a high
of 2.619 in the case of the ETG basis. The bond
distance obtained from the DZP basis set is intermediate between the other two sets, though closer
to the ECP basis results. The AsH bond distance,
on the other hand has the smallest value in the DZP
basis and largest value in the ETG basis. The ECP
results are intermediate between the other two results. Contrary to the bond distance, the bond angle
at the central Ga atom remains unchanged and is
very close to a tetrahedral geometry. The bond angles (HAsH) at the outer heavy atom (As) vary from

Bond angles (deg)

AsGaAs
109.49
109.52
109.45

HAsGa

HAsH

112.70
112.41
113.77

105.97
106.41
104.50

104.5 in the ETG basis to 106.4 in the DZP basis.

The ECP basis gives an intermediate value. It appears that the outer angles made by H atoms have
a tendency to deviate from the tetrahedral geometry. The HAsGa angle varies from 112.4 in the DZP
basis set to 113.8 in the ETG basis. The ECP basis
results are intermediate between the other two.
The optimized geometrical parameters in the
case of the Ga-rich AsGa4 H3
12 cluster obtained from
different basis sets are listed in Table V. The DZP basis set gives the smallest value for the GaAs bond
distance, which is about 0.024 shorter than the
corresponding value in the case of the As-rich cluster GaAs4 H3+
12 (Table IV). The maximum variation in
the GaAs bond distance due to the basis set in the
case of the AsGa4 H3
12 cluster is 0.027 (Table V).
The GaH bond distance also has the smallest
value in the case of the DZP basis and the largest
value in the case of the ETG basis. The GaAsGa
angle at the central As atom remains essentially
unchanged and is nearly tetrahedral. The angles
formed by the outer H atom (HGaH), though nearly
equal in all three basis sets, are slightly less than the
tetrahedral angle. Similarly the angle HGaAs made
by the H atom and the central As atom at the Ga
atom is slightly higher than the tetrahedral angle
even though all three basis sets give more or less the
same value.

TABLE V
Ab initio HF geometry optimization for AsGa4 H3
12 molecule.
Bond distances ()
Basis set
ECP
DZP
ETG

568

Bond angles (deg)

GaAs

GaH

GaAsGa

HGaAs

HGaH

2.548, 2.547
2.529
2.556

1.647
1.639
1.660

109.53
109.54
109.45

111.41
111.17
111.59

107.44
107.73
107.44

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GaAs CLUSTERS: THE GEOMETRY

FIGURE 7. As4 Ga4 H18 molecule in Td geometry. The

parameters are optimized using DZP basis set.

FIGURE 6. H3 AsGaH3 molecule in Td geometry. The

parametes are optimized using DZP basis set.

THE B3 ABA3 SYSTEMS

AsGaH6
The H3 AsGaH3 molecule, shown in Figure 6, represents the smallest member of the GaAs cluster
with equal number of Ga and As atoms. This cluster
is also small enough to lend itself to EC calculations.
The optimized geometry of this molecule obtained
from different basis sets and including the EC effect
via MP2 calculation are listed in Table VI. The calculated GaAs bond distance varies widely with
basis set, having the lowest value in the case of the
DZP basis set and the largest value in the case of
the ECP basis set. The DZP basis set also gives the
lowest value for the AsH and GaH bond distances, followed by the ECP and the ETG basis sets.
However, the magnitude of the changes in the values of AsH and GaH distances due to the basis
sets is much less dramatic than that noted in the
case of the GaAs bond distance. The effect of EC
on the geometry is largest in the ECP basis set and
smallest in the ETG basis set. In the case of the ECP
basis set, EC shortens the GaAs bond distance by

0.14 compared to 0.065 in the DZP basis and

0.008 in the ETG basis set. However, the EC effect actually increases the AsH and GaH bond
distances except for the GaH bond distance in the
DZP basis set where EC does not appear to have
any effect. Unlike the bond distances, the HGaH
and HAsH angles seem to be rather insensitive to
the basis set as well as EC. In all calculations, the
HGaH angles are much larger than the tetrahedral
angle (relaxed), and HAsH angles are much shorter
(strained) than the tetrahedral angle, as listed in Table VI. The HAsGa and HGaAs angles are also far
from tetrahedral angle, as shown in Figure 6. The
parameters shown in Figure 6 are from the DZP basis set calculation. The calculated GaAs distance
for X3 6 state of diatomic GaAs from experimental measurement is 2.53 [18] and that from an ab
initio multireference single and double (MRD) configuration interaction (CI) study on GaAs dimer is
2.60 [19]. The nearest neighbor distance at T =
300 K for the zinc blende crystalline state of GaAs
is 2.44793 [2, 12]. The best calculated GaAs
distance (DZP; MP2) is about 0.24 larger than
the corresponding distance in crystalline GaAs, and
about 0.135 larger than that observed for diatomic
GaAs in gas phase. However, the present best value

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KORAMBATH, SINGARAJU, AND KARNA

TABLE VI
Ab initio HF and MP2 geometry optimization for AsGaH6 molecule.
Bond distances ()

Bond angles (deg)

Basis set

GaAs

AsH

GaH

HGaAs

HAsGa

HAsH

HGaH

ECP
ETG
DZP
ECP; MP2
ETG; MP2
DZP; MP2

2.893
2.781
2.750
2.756
2.773
2.685

1.505
1.526
1.491
1.527
1.540
1.495

1.579
1.604
1.576
1.589
1.609
1.576

95.06
96.37
96.41
95.85
96.02
96.01

119.81
118.78
119.10
120.10
119.89
119.89

97.43
98.76
98.35
97.05
97.32
97.33

119.23
118.78
118.77
118.97
118.92
118.92

is only 0.085 larger than the MRDCI result for

GaAs.
H9 As3 GaAsGa3 H9
The molecular cluster Ga4 As4 H18 obtained from
replacing the H atoms from the structure shown in
Figure 6 and terminating the valency of the outer
heavy atoms by H atoms is shown in Figure 7.
This cluster represents the smallest system in which
the central Ga/As atoms are appropriately bonded
to four As/Ga hetero atoms. Of course, again, the
outer heavy atoms have two different chemical environments around them. They are each bonded
to one (central) hetero atom and three H atoms.
Accordingly, only the central Ga and As atoms experience a somewhat realistic chemical environment
corresponding to the GaAs crystal. The optimized
bond lengths and bond distances for this cluster
obtained from different basis sets are listed in Table VII. As expected, the central GaAs bond drastically differs from the outer Ga/AsAs/Ga bonds.
The latter distances are much too large compared to
the former, which is closer to the crystalline value
of RGaAs = 2.448 . The central GaAs bond distance varies from a low of 2.312 in the case of the
DZP basis set to a high of 2.416 in the case of the

ETG basis set. The ECP basis set gives an intermediate value, larger by about 0.03 compared to the
DZP basis set. The trend is somewhat different for
outer Ga/AsAs/Ga bond distances, which have
the highest magnitude in the case of the ECP basis,
although the DZP basis set again gives the smallest value. The outer Ga/AsAs/Ga values are much
closer to each other in different basis sets. We note a
trend here for the outer heavy-atom bond distances.
The termination of the valency by the H atoms appears to weakens the Ga/AsAs/Ga bonding. This
results in the elongation of outer GaAs bonds.
Contrary to what was noted in other clusters,
the bond angles in the Ga4 As4 H9 exhibit a large
variation due to the basis set. Specifically, the AsGaAs angle at the central Ga atom varies from a
low 89 in the case of the ETG basis set to a high
of about 104 in the case of the DZP basis set. The
ECP basis set gives somewhat of an intermediate
value. It appears that both the ECP and the ETG basis sets place greater strain around the central Ga
atom. The GaAsGa bond angle is relaxed, deviating from a tetrahedral geometry by around 7 to
10 , with smallest and the largest deviation given by
the ETG and the ECP basis sets, respectively. Since
each heavy atom is surrounded by its compensating hetero atoms, the overall valency of each heavy

TABLE VII
Ab initio HF Geometry Optimization for As4 Ga4 H18 molecule.
Bond distances ()

Bond angles (deg)

Basis

GaAs

AsH

GaH

AsGaAs

GaAsGa

ECP
DZP
ETG

2.341, 2.680, 2.709

2.312, 2.602, 2.610
2.417, 2.647, 2.655

1.489, 1.503
1.478, 1.490
1.531, 1.506

1.577, 1.610
1.586, 1.609
1.583, 1.632

96.6, 120.4
103.8, 114.7
89.5, 125.6

119.9, 89.5
117.4, 99.5
115.9, 78.2

570

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GaAs CLUSTERS: THE GEOMETRY

FIGURE 8. As3 Ga3 H12 molecule in Td geometry (chair conformation). The parameters are optimized using DZP basis
set.

atom is satisfied. The reason for the deviation of the

central atom geometry from a tetrahedral symmetry is not clear to us. It is possible that the outer H
atoms place sufficient strain on the cluster to distort
the symmetry. In such a case, increasing the size of
the cluster may produce a less distorted and more
realistic structure. At the same time, a lack of EC
in the theoretical treatment of this cluster may also
have resulted in the noted geometry deformation,
although the EC effect noted on the smaller cluster
suggest the contrary.
As3 Ga3 H12
The As3 Ga3 H12 system shown in Figure 8 is
unique in the sense that each heavy atom is bonded

to two heavy hetero atoms and two hydrogen

atoms, forming a ring structure. It has two conformations: a boat and a chair, as shown in Figure 8
(chair). It is interesting to note that the two conformations are almost degenerate (1E = 0.0009 eV)
at the HF level of calculations. The results of the
geometry optimization for this cluster are given in
Table VIII. It is noted from the table that the Ga
As distance is close to the experimental gas-phase
value of 2.53 [18]. Compared to that noted in other
clusters, the GaAs distance in this ring structure is
closer to the crystalline value of 2.447 . One further notes a rather small variation of GaAs bond
distance due to basis sets. The GaH bond distance
is somewhat shorter than that calculated in the case
of the GaH
4 cluster (Table II). The calculated As

TABLE VIII
Ab initio geometry optimization for As3 Ga3 H12 molecule.
Bond distances ()
Basis set
ECP
DZP
ETG

Bond angles (deg)

GaAs

AsH

GaH

AsGaAs

GaAsGa

2.561
2.543
2.591

1.505, 1.504
1.491, 1.492
1.516, 1.517

1.571
1.568
1.589, 1.584

100.28
100.62
96.87

126.47
124.73
122.98

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TABLE IX
Ab initio HF geometry optimization (DZP basis set) for GaAs molecular clusters.
Bond distances ()
Molecule
AsH+
4
GaH
4
AsGaH6
GaAs4 H3+
12
AsGa4 H3
12
Ga3 As3 H12
Ga4 As4 H18

AsH

GaH

AsGa

AsGaAs

GaAsGa

1.474
1.491
1.481
1.491
1.478, 1.491

1.632
1.576
1.639
1.568
1.568, 1.609

H bond distance, on the other hand, is much closer

to that obtained in the case of the AsH+
4 cluster (Table III). Also the GaH and AsH bond lengths show
small variation due to basis set.
Once again, it is noted that the AsGaAs bond
angles are somewhat strained by 7 to 10 with respect to tetrahedral symmetry. At the same time, the
GaAsGa bond angles are relaxed by 13 to 17 with
respect to the tetrahedral geometry. The parameters
shown in Figure 8 are optimized using the DZP basis set.

Summary
As a first step toward studying the microscopic
structure and properties of point defects in GaAs,
we have investigated the stability and geometrical
features of finite-size atomic clusters composed of
Ga and As atoms. The present study has revealed
new insights into the stability of GaAs clusters.
First, it has demonstrated that in the absence of any
charge (q = 0) only a 1:1 composition of Ga and As
atoms in Gam Asn (m = n) cluster leads to a stable
nearly tetrahedral geometry. Any other composition
Gam Asn with m 6= n requires addition or removal
of electrons from the system in order to stabilize
it. Second, the charge compensation, i.e., addition
or removal of electrons, appears to work nicely for
smaller clusters. However, as the size of the cluster Gam Asn (m 6= n) increases, the large amount of
charge required to maintain a group IV type of electronic configuration tends to destabilize the cluster.
This observation can be used to predict the extent of electrical and microscopic structural changes
of GaAs semiconductors due to point defects. From

572

Bond angles (deg)

2.750
2.553
2.529
2.543
2.312, 2.610, 2.602

109.5
100.6
103.8, 114.7

109.6
124.7
117.4, 99.5

the above observations, one expects that a Ga vacancy (V Ga ) in GaAs will create an As-rich domain
that will try to stabilize (a) by relaxing the network
around the vacancy, (b) by losing extra electrons
(i.e., capture holes), or (c) by a combination of both
(a) and (b). A similar behavior will be expected in
the presence of As at Ga (AsGa ) antisite. On the other
hand, in Ga-rich (V As ) materials, one would expect
the system to stabilize by (a) relaxing the network
similar to that in the case of the As-rich sample,
(b) by capturing electrons, thus creating holes some
where else in the lattice, or (c) by a combination of
both (a) and (b).
In all cases, however, in the presence of vacancies
or antisites the lattice will experience deformation
and/or will create electronhole pairs. A more detailed discussion of this phenomenon will be presented in a subsequent work.
For the geometry optimization of the GaAs clusters, it turns out that the DZP basis provides the
best choice among the three basis sets used in this
study. The geometry of all the stable tetrahedral
clusters obtained from the DZPHF calculations are
collected in Table IX for comparison. In general, for
charged clusters, the central atom retains tetrahedral symmetry in different basis sets as well as EC
calculations. The DZP basis bond distances are relatively smaller than the other two basis sets. The
EC effect has a larger influence on the ECP basis
set compared to the other two. The uncharged clusters show deviation from tetrahedral geometry. In
general, the angles at the Ga atom are strained (less
than tetrahedral) and the angles at the As atom are
relaxed (greater than tetraredral) for 1:1 GaAs clusters. This may be due to the fact that the outer atoms
are terminated with hydrogen atoms rather than As

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GaAs CLUSTERS: THE GEOMETRY

or Ga atoms, which would have been the case in a
real crystalline environment.
ACKNOWLEDGMENTS
P.P.K. would like to acknowledge the National
Research Council for a Resident Research Associate
award. Computations were made possible by the
award of computer time at the Albuquerque High
Performance Computing Center (AHPCC), Maui
High Performance Computing Center (MHPCC),
and by the ASC-MSRSC DOD-HPC MO project.
Fruitful discussions with Prof. Henry Kurtz, Prof.
Sigrid Peyerimhoff, and Prof. S. Pantelides have
benefited this work.

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