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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 Hartree–Fock (HF) and
second-order Møller–Plesset 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: 563–573, 2000

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

Introduction

G

allium–arsenide (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, 563–573 (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

However. as shown in Figure 1. for Ga atom to form four tetrahedral (sp3 ) bonds. Structure (ii). 7]. AND KARNA number of Ga (I = 32 ) and As (I = 32 ) atoms. it would be charged in a tetrahedral geometry. 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]. 2. Ga has three valence electrons with the electronic configuration given by (core) 4s2 4p1 . As will be discussed here. However. In view of the importance of point defects in GaAs and a lack of reliable data concerning their nature and properties. they do not describe the localized properties such as the spin distribution and hyperfine interaction. NO. Similarly for the As atom to form four tetrahedral (sp3 ) bonds. preserving a Td symmetry of a GaAs cluster depends upon the number of binary atoms as well as the total charge on the clusters. While structure (ii) would not require external charges to maintain four-coordinated geometry. (i) or (ii). some comments on the nature of the covalent bond- FIGURE 1. (a) Model AB4 structure [structure (i)]. an electron needs to be removed from its valence shell. It is possible to extract useful information from ESR data with the help of quantum mechanical calculations. The core in both cases consists of the inner-shell (n = 1. For small clusters. Arsenic has five valence electrons with its electronic configuration given by (core) 4s2 4p3 . B = Ga. detailed study of these defects via ab initio quantum mechanical methods is deemed highly desirable and timely. the effects of basis set and electron correlation on the geometry have also been investigated. This simple valency consideration allows one to successively build tetrahedral atomic clusters consisting of Ga and As atoms. a potential difficulty in studying point defects in GaAs using an atomic cluster approach is the ability to generate realistic model structures. (b) Model B3 A–BA3 structure [structure (ii)]. Starting from either of the two prototypical structures. As. it is immediately clear that structure (i) has an unequal number of Ga and As atoms. 3) electrons. maintains the 1:1 ratio of Ga to As and does not require external charges in order to be in stable tetrahedral geometry.KORAMBATH. electrons need to be added (m > n) or removed (m < n) to obtain a tetrahedral geometry. SINGARAJU. The latter condition is intimately related to the former. However. and some attempts have been made in this direction in the past [9. While such approaches are reasonable for calculating band energy and also super-cell cluster stability. one can successively build larger clusters of GaAs. 77. 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]. 10] place serious limitation on the reliability of the results. The smallest prototypical structures providing the basis for building tetrahedral GaAs structures. 564 VALENCY AND BONDING CONSIDERATIONS Before proceeding to build molecular clusters and optimize geometry. an extra electron needs to be added to its valence shell. A realistic model of GaAs in the cluster approach must accurately represent the local symmetry and the structure of the crystal. as discussed above. 10]. Therefore. VOL. as a first step we have investigated the stability and structural properties of finite size clusters consisting of Ga and As atoms. 12]. the extra electron required by the former is supplied by the latter. on the other hand. 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. For a tetrahedral cluster Gan Asn consisting of an equal number of Ga and As atoms. and there is no need of extrinsic charge to be added or removed. 2 . the stable structures do not often retain a tetrahedral (Td ) symmetry. When constructing atomic clusters of GaAs with a minimal number of atoms. for a cluster like Gam Asn (m 6= n) with unequal number of Ga and As atoms. where A. theoretical approaches used in these calculations [9. 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. are (i) AB4 and (ii) B3 A–BA3 . Therefore. Therefore. it is useful to discuss the valency and the nature of chemical bonds around Ga and As atoms. However.

1(a)].324 0.628 19131.754289 −0. having only three valence electrons.561924 0.876 6377.860889 As d Coef.000456 0. 2). These were: (i) a relativistic compact effective potential (RCEP) [14]. [16] for Ga and As are listed in Table I.636163 −1.000353 0.000000 0. The optimized structures of the neutral and negatively charged TABLE I Extended even-tempered Gaussian (ETG) basis set for Ga and As.609428 0. 2.209815 0. The Ga atom. 0. 15].244 8.352162 0. 2. and (iii) a polarized even-tempered Gaussian (ETG) basis set [16].501311 −0. The exponents and contraction coefficients of the ECP and the DZP basis sets are available in the literature [14.233898 0. also known as effective core potential (ECP). with its five valence electrons.005631 0.646384 −0. contributes 0.000000 −0. 0. Model Structures Guided by the above considerations.091494 0. we started with the two prototypical structures.790018 −0.108 0.000000 a Contraction p Coef.279083 0. 2).096571 0.002245 0.630390 −0. AsH4 .650 172186. AsH4 These molecules belong to the prototype cluster structure AB4 [Fig.006536 0.588 236.25e to each of the four tetrahedral bonds.827793 0. Additionally. in the ideal condition. 1(a)]. The resulting structure H9 As3 GaAsGa3 H9 is shown in Figure 7. 516560. The orbital exponents and the contraction coefficients of the ETG basis set taken from Ref. The larger clusters.748 2.550925 0. We calculated the geometry of tetrahydrides of Ga and As.764 708.247189 1. 8) to study a ring (closed) structure. will contribute 1.049464 0. 1(b)] is H3 GaAsH3 (Fig.000547 0.083890 0.805843 0.732 26.523260 d Coef.675742 −1.258969 0.510399 0.021830 0. 1.916 0.196 78.505871 s Coef. COMPUTATIONAL METHODS AND BASIS SETS Calculations were performed using ab initio Hartree–Fock (HF) and second-order Møller–Plesset (MP2) theory with the help of the GAMESS [13] quantum chemistry package. p Coef. The As atom. 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.75e to each of its four tetrahedral bonds.000000 −0.a Ga Exponent s Coef.402947 1. The next larger cluster was built by replacing the H atoms in Figure 6 with appropriate heavy (Ga/As) atoms.002653 0. Therefore.842206 −0.383392 scheme = s (9. Three different basis sets were used in the calculations. Results THE AB4 SYSTEMS + The GaH4 . INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 565 . These structures are shown in Figures 4 and 5.880 57395. d (3. 0.315092 0.000000 1.000174 0. 2 and 3) is of the type AB4 [Fig. GaH− 4 .186478 0.972 0.234260 0. a cluster with composition (H2 Ga—AsH2 )3 was also constructed (Fig.001508 0.720476 0. (ii) The smallest cluster for the second prototypical-type structure B3 A–BA3 [Fig.419702 0.292 2125.501562 0.385246 0. 0.287720 0.018437 0.000148 0. (i) The first set consisting of a central Ga/As atom coordinated to four H atoms (Figs. 6). 2.249136 0.GaAs CLUSTERS: THE GEOMETRY ing between Ga and As atoms still seem to be in order. a Ga—As bond in structure (ii) tetrahedral cluster is not fully covalent but has partial ionic character represented by Gaδ− —Asδ+ .015583 0. (ii) a double-zeta polarization (DZP) (DZV + 3d functions on heavy atoms and 1p function on light H atoms) [15].025463 0.000304 0.000000 1.001768 0. p (6.079839 0. 1.043105 0. 1).

645 1.480 1. 77.47 109.634 1. The corresponding charged clusters.663 Å [17]. The optimized structures of neutral and positively charged AsH4 using the DZP basis set are shown in Figure 3.49 109. SINGARAJU. aR e for X3 6 − state of As—H is 1.632 1.477 109.628 1.509 1.625 109.48 109.47 109.485 1. (b) GaH− 4 molecule in Td geometry. 2 .5344 Å [17].49 109.48 109. The neutral AsH4 cluster also has a triangular pyramidal equilibrium structure with three As—H bonds in a plane with the As atom and the TABLE II Ab initio HF and MP2 geometry optimization for a GaH− 4 molecule.474 1.49 109. VOL. are stable in tetrahedral geometry.635 1. a Ab initio geometry optimization for AsH+ 4 molecule. The fourth H atom is located perpendicularly above the GaH3 plane at distance twice the other Ga—H distance.KORAMBATH. (a) GaH4 molecule with three H atoms and FIGURE 3. MP2 1. The parameters are optimized using DZP basis set.481 1. It is apparent that neutral tetrahydrides of Ga and As atoms do not have a stable tetrahedral structure. MP2 DZP DZP. clusters of GaH4 using the DZP basis set are shown in Figure 2. AND KARNA (a) (a) (b) (b) FIGURE 2.49 109.48 109.48 aR 566 e for X3 6 − state of Ga—H = 1.491 1. (a) AsH4 molecule with three H atoms and a Ga atom in a plane and the fourth H atom in a perpendicular plane. MP2 ECP + PF on Ga and H.48 109. an As atom in a plane and the fourth H atom in a perpendicular plane. The parameters are optimized using DZP basis set. In this case the fourth Ga—H bond represents an antibonding-type orbital.642 1. The parameters are optimized using DZP basis set. The parameters are optimized using DZP basis set. MP2 ECP + PF on As and H. MP2 DZP DZP.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. (b) AsH+ 4 molecule in Td geometry.48 109. NO.480 1. TABLE III Basis set Re (Å) Angle (deg) Basis set Re (Å) 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 1.641 1.48 109. The neutral GaH4 has a pyra- midal structure with three H atoms in a plane containing the Ga atom. on the other hand.49 109.

the As—H bond length increases by 0.01 Å than those with PF on both heavy as well as the light atoms.013 Å but leaves the HGaH angle basically unchanged. A somewhat similar effect is noted on the geometry of AsH+ 4 cluster due to basis sets. Also. The ECP basis set augmented with polarization functions (PF) on the As alone gives an As—H bond length that is slightly larger by 0. 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. An ECP basis set calculation on neutral AsH4 cluster resulted in a trigonal pyramidal structure with three H atoms at 1. The all-electron DZP basis set gives an As—H bond distance that is too small by about 0. fourth H atom in a perpendicular plane. The parameters are optimized using DZP basis set.007 Å compared to that obtained with the ECP basis set. 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- INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 567 .003 Å. On the other hand. MP2) is about 0. Inclusion of electron correlation (EC) via MP2 with the ECP basis set reduces the Ga—H bond length by about 0. the bond angles. and for the ECP basis set with PF on As and H. However. the optimized equilibrium geometry of the two charged clusters has a tetrahedral symmetry.038 Å shorter FIGURE 5. For GaH− 4 cluster. inclusion of EC via MP2 with the DZP basis set reduces the bond distance only by 0. the EC effect with the DZP basis set increases the As—H bond distance by about 0.72 Å shorter than that of the other three As—H atom distances. the bond distance is 0. the best calculated bond distance in the case of AsH+ 4 cluster obtained (DZP.647 Å. 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.05 Å shorter than the corresponding value for the diatomic AsH species in its X3 6 − state. seem to be rather insensitive to the choice of the basis set and EC.007 Å but leaves the angles unchanged. Also listed in the tables are the observed bond distances of X3 6 − state of the diatomic species Ga/As—H [17]. AsGa4 H3− 12 molecule in Td geometry.519 Å pointing to the corners of the base triangle and the fourth atom at the apex of the pyramid at 4. The best calculated Ga—H bond distance (DZP. MP2) is about 0. GaAs4 H3+ 12 molecule in Td geometry. The effect of EC on the geometry of AsH+ 4 is different from that noted in the + case of GaH− 4 . similar to that in the case of GaH− 4 .GaAs CLUSTERS: THE GEOMETRY FIGURE 4.005 Å. 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. as noted from Table III. However. respectively. In the case of AsH4 . the changes in the bond angles and bond distances due to the basis sets are marginal.

2. SINGARAJU.53 109. It appears that the outer angles made by H atoms have a tendency to deviate from the tetrahedral geometry.5◦ in the ETG basis to 106.660 109.8◦ in the ETG basis.4◦ in the DZP basis. −2. the Ga—As bond distance varies from a low of 2. 2 .618.639 1.45 111. Bond distances (Å) Basis set ECP DZP ETG 568 Bond angles (deg) Ga—As Ga—H Ga—As—Ga H—Ga—As H—Ga—H 2. 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.516 ing the valency of the outer atoms with H atoms as shown in Figures 4 and 5.73 107. 2. Contrary to the bond distance. the bond angle at the central Ga atom remains unchanged and is very close to a tetrahedral geometry. 2.77 105.41 111.45 H—As—Ga H—As—H 112.44 107. Both these clusters exhibit tetrahedral symmetry around the central heavy atom. The only clusters exhibiting stable geometry 3− were the GaAs4 H3+ 12 and AsGa4 H12 species. though nearly equal in all three basis sets.97 106. AND KARNA TABLE IV Ab initio HF geometry optimization for GaAs4 H3+ 12 molecule.17 111. 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. TABLE V Ab initio HF geometry optimization for AsGa4 H3− 12 molecule.556 1. are slightly less than the tetrahedral angle.41 104. respectively.551. the two clusters did not converge to a stable geometry. The ECP results are intermediate between the other two results.558 2. In order to check the stability of the charged clusters.553 2.481 1. The As—H bond distance. 1.529 2. though closer to the ECP basis results.52 109.547 2.490. The angles formed by the outer H atom (HGaH). NO. The optimized GaAs4 H3+ 12 and AsGa4 H3− 12 clusters using the DZP basis set are shown in Figures 4 and 5.50 104. The HAsGa angle varies from 112. The DZP basis set gives the smallest value for the Ga—As bond distance. 1.KORAMBATH. on the other hand has the smallest value in the DZP basis and largest value in the ETG basis.41 113. 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.59 107.44 VOL. respectively. The bond angles (HAsH) at the outer heavy atom (As) vary from Bond angles (deg) As—Ga—As 109. and -3 for AsGa4 H12 cluster.49 109.70 112. which is about 0.551 Å in the case of the ECP basis to a high of 2.54 109. and 3 for GaAs4 H12 and charges q = −1.4◦ in the DZP basis set to 113.517. 77. The ECP basis results are intermediate between the other two. In their charge neutral state (q = 0). The Ga—H 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.548. The maximum variation in the Ga—As bond distance due to the basis set in the case of the AsGa4 H3− 12 cluster is 0.619 1.647 1. we performed geometry optimization with charges q = 1. The bond distance obtained from the DZP basis set is intermediate between the other two sets. Bond distances (Å) Basis set ECP DZP ETG Ga—As As—H 2.024 Å shorter than the corresponding value in the case of the As-rich cluster GaAs4 H3+ 12 (Table IV). The GaAsGa angle at the central As atom remains essentially unchanged and is nearly tetrahedral. 2.489 1. The ECP basis gives an intermediate value.027 Å (Table V).619 Å in the case of the ETG basis. For the Asrich cluster.

The parametes are optimized using DZP basis set. FIGURE 6. The parameters are optimized using DZP basis set.135 Å larger than that observed for diatomic GaAs in gas phase. the EC effect actually increases the As—H and Ga—H bond distances except for the Ga—H bond distance in the DZP basis set where EC does not appear to have any effect. The best calculated Ga—As distance (DZP. the magnitude of the changes in the values of As—H and Ga—H distances due to the basis sets is much less dramatic than that noted in the case of the Ga—As bond distance.14 Å compared to 0.GaAs CLUSTERS: THE GEOMETRY FIGURE 7. MP2) is about 0. The DZP basis set also gives the lowest value for the As—H and Ga—H bond distances. H3 AsGaH3 molecule in Td geometry. Unlike the bond distances.065 Å in the DZP basis and 0. However. However.60 Å [19]. shown in Figure 6. the HGaH angles are much larger than the tetrahedral angle (relaxed). the HGaH and HAsH angles seem to be rather insensitive to the basis set as well as EC. and about 0. represents the smallest member of the GaAs cluster with equal number of Ga and As atoms. as shown in Figure 6. as listed in Table VI. THE B3 A–BA3 SYSTEMS AsGaH6 The H3 AsGaH3 molecule. followed by the ECP and the ETG basis sets. the present best value INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 569 . 12].008 Å in the ETG 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. EC shortens the Ga—As bond distance by 0.24 Å larger than the corresponding distance in crystalline GaAs. However. The calculated Ga—As bond distance varies widely with basis set. The parameters shown in Figure 6 are from the DZP basis set calculation. The optimized geometry of this molecule obtained from different basis sets and including the EC effect via MP2 calculation are listed in Table VI.53 Å [18] and that from an ab initio multireference single and double (MRD) configuration interaction (CI) study on GaAs dimer is 2. The HAsGa and HGaAs angles are also far from tetrahedral angle. The calculated Ga—As distance for X3 6 − state of diatomic GaAs from experimental measurement is 2. and HAsH angles are much shorter (strained) than the tetrahedral angle. The effect of EC on the geometry is largest in the ECP basis set and smallest in the ETG basis set. In all calculations.44793 Å [2. The nearest neighbor distance at T = 300 K for the zinc blende crystalline state of GaAs is 2. This cluster is also small enough to lend itself to EC calculations. As4 Ga4 H18 molecule in Td geometry. In the case of the ECP basis set.

589 1. The GaAsGa bond angle is relaxed.2 570 VOL.01 119. The optimized bond lengths and bond distances for this cluster obtained from different basis sets are listed in Table VII. 2 .503 1.680.773 2.647. The ECP basis set gives an intermediate value.89 119.526 1.495 1. the outer heavy atoms have two different chemical environments around them. The ECP basis set gives somewhat of an intermediate value. 1.312 Å in the case of the DZP basis set to a high of 2.03 Å compared to the DZP basis set.632 96. 2. 2.9.4 103. respectively. They are each bonded to one (central) hetero atom and three H atoms.78 118.604 1.583. 1.06 96. MP2 2.7 89.77 118. although the DZP basis set again gives the smallest value.41 95. This cluster represents the smallest system in which the central Ga/As atoms are appropriately bonded to four As/Ga hetero atoms. NO. Accordingly.92 is only 0.89 97.KORAMBATH. 1.81 118. The termination of the valency by the H atoms appears to weakens the Ga/As–As/Ga bonding.655 1.491 1.37 96.448 Å.085 Å larger than the MRDCI result for GaAs. The latter distances are much too large compared to the former.540 1.602. Since each heavy atom is surrounded by its compensating hetero atoms.416 Å in the case of the ETG basis set.92 118. The outer Ga/As–As/Ga values are much closer to each other in different basis sets.10 119.32 97. deviating from a tetrahedral geometry by around 7◦ to 10◦ .33 119. the overall valency of each heavy TABLE VII Ab initio HF Geometry Optimization for As4 Ga4 H18 molecule.05 97.5 117. 120. Bond distances (Å) Bond angles (deg) Basis set Ga—As As—H Ga—H H—Ga—As H—As—Ga H—As—H H—Ga—H ECP ETG DZP ECP. the central Ga—As bond drastically differs from the outer Ga/As–As/Ga bonds. larger by about 0.893 2.6. 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. 77.756 2.02 96.609 1.85 96. The central Ga—As bond distance varies from a low of 2. SINGARAJU.490 1.586. 2. which is closer to the crystalline value of RGa—As = 2.478. 1.576 95.576 1.610 2. which have the highest magnitude in the case of the ECP basis. MP2 DZP.781 2. 114.78 119. 2. It appears that both the ECP and the ETG basis sets place greater strain around the central Ga atom.577.709 2.6 119. This results in the elongation of outer Ga—As bonds. Of course.8.76 98. As expected.9. the bond angles in the Ga4 As4 H9 exhibit a large variation due to the basis set.579 1.23 118.527 1.505 1.531. with smallest and the largest deviation given by the ETG and the ECP basis sets.417.750 2. AND KARNA TABLE VI Ab initio HF and MP2 geometry optimization for AsGaH6 molecule. 99.312. The trend is somewhat different for outer Ga/As–As/Ga bond distances.35 97. 125.4. 1.610 1. Specifically. Bond distances (Å) Bond angles (deg) Basis Ga—As As—H Ga—H As—Ga—As Ga—As—Ga ECP DZP ETG 2.506 1. 89.5.43 98.5 115.489. We note a trend here for the outer heavy-atom bond distances. 2.685 1. again. 2. MP2 ETG. 1.97 118. Contrary to what was noted in other clusters. 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. 78.609 1. only the central Ga and As atoms experience a somewhat realistic chemical environment corresponding to the GaAs crystal.341.10 120.

It is possible that the outer H atoms place sufficient strain on the cluster to distort the symmetry. increasing the size of the cluster may produce a less distorted and more realistic structure. 1. In such a case. 1.GaAs CLUSTERS: THE GEOMETRY FIGURE 8. The reason for the deviation of the central atom geometry from a tetrahedral symmetry is not clear to us. It has two conformations: a boat and a chair.73 122. Bond distances (Å) Basis set ECP DZP ETG Bond angles (deg) Ga—As As—H Ga—H As—Ga—As Ga—As—Ga 2. The parameters are optimized using DZP basis set. the Ga–As distance in this ring structure is closer to the crystalline value of 2. The calculated As– TABLE VIII Ab initio geometry optimization for As3 Ga3 H12 molecule. It is noted from the table that the Ga– As distance is close to the experimental gas-phase value of 2.491. One further notes a rather small variation of Ga–As bond distance due to basis sets.505.447 Å.571 1.87 126.568 1.517 1.591 1.53 Å [18].62 96. Compared to that noted in other clusters. It is interesting to note that the two conformations are almost degenerate (1E = 0.492 1.28 100. forming a ring structure.98 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 571 . as shown in Figure 8 (chair).0009 eV) at the HF level of calculations. 1.543 2.584 100.516. The Ga–H bond distance is somewhat shorter than that calculated in the case of the GaH− 4 cluster (Table II). although the EC effect noted on the smaller cluster suggest the contrary. 1. atom is satisfied. The results of the geometry optimization for this cluster are given in Table VIII. At the same time. As3 Ga3 H12 molecule in Td geometry (chair conformation). a lack of EC in the theoretical treatment of this cluster may also have resulted in the noted geometry deformation.561 2.504 1.589. 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.47 124.

5 the above observations.529 2.553 2. appears to work nicely for smaller clusters. On the other hand. 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. 114. 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. 77.610.481 1. or (c) by a combination of both (a) and (b). 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.491 1.7 109. A more detailed discussion of this phenomenon will be presented in a subsequent work. From 572 Bond angles (deg) 2. as the size of the cluster Gam Asn (m 6= n) increases.474 1. For the geometry optimization of the GaAs clusters. AND KARNA TABLE IX Ab initio HF geometry optimization (DZP basis set) for GaAs molecular clusters. the central atom retains tetrahedral symmetry in different basis sets as well as EC calculations. on the other hand.5 100. capture holes). the charge compensation. it is noted that the AsGaAs bond angles are somewhat strained by 7◦ to 10◦ with respect to tetrahedral symmetry.543 2. The uncharged clusters show deviation from tetrahedral geometry.312.639 1.e. however. In general.. 2 .750 2. The present study has revealed new insights into the stability of GaAs clusters.602 109. is much closer to that obtained in the case of the AsH+ 4 cluster (Table III). Any other composition Gam Asn with m 6= n requires addition or removal of electrons from the system in order to stabilize it.e.6 124. This observation can be used to predict the extent of electrical and microscopic structural changes of GaAs semiconductors due to point defects.478. In all cases. (b) by losing extra electrons (i. NO. First.. i. Bond distances (Å) Molecule AsH+ 4 GaH− 4 AsGaH6 GaAs4 H3+ 12 AsGa4 H3− 12 Ga3 As3 H12 Ga4 As4 H18 As—H Ga—H As—Ga As—Ga—As Ga—As—Ga 1.568 1. Also the Ga–H and As–H bond lengths show small variation due to basis set. SINGARAJU. 2. A similar behavior will be expected in the presence of As at Ga (AsGa ) antisite.8. 2. addition or removal of electrons. In general.6 103. The parameters shown in Figure 8 are optimized using the DZP basis set. Once again. for charged clusters.7 117. Second. Summary As a first step toward studying the microscopic structure and properties of point defects in GaAs. The geometry of all the stable tetrahedral clusters obtained from the DZP–HF calculations are collected in Table IX for comparison. it turns out that the DZP basis provides the best choice among the three basis sets used in this study.576 1. The EC effect has a larger influence on the ECP basis set compared to the other two.568.KORAMBATH. thus creating holes some where else in the lattice. the large amount of charge required to maintain a group IV type of electronic configuration tends to destabilize the cluster. we have investigated the stability and geometrical features of finite-size atomic clusters composed of Ga and As atoms.609 H bond distance. the GaAsGa bond angles are relaxed by 13◦ to 17◦ with respect to the tetrahedral geometry.632 1. However. At the same time.4. 99. one would expect the system to stabilize by (a) relaxing the network similar to that in the case of the As-rich sample. The DZP basis bond distances are relatively smaller than the other two basis sets. or (c) by a combination of both (a) and (b). in the presence of vacancies or antisites the lattice will experience deformation and/or will create electron–hole pairs. in Ga-rich (V As ) materials.491 1. 1. (b) by capturing electrons. This may be due to the fact that the outer atoms are terminated with hydrogen atoms rather than As VOL. 1.491 1.

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