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J. Phys. C : Solid State Phys., Vol. 12, 1979. Printed in Great Britain. @ 1979

A large unit cell semiempirical molecular orbital approach to

the properties of solids I. General theory

A H Harker and F P Larkins?

Theoretical Physics Division, AERE, Harwell, Didcot, Oxon OX11 ORA, UK

Received 24 July 1978

Abstract. Two semiempirical crystal orbital schemes are outlined for the calculation of the
properties of perfect and defective solids. Both use periodic boundary conditions with a
large unit cell (LUC) to map special points of the Brillouin zone onto the point k = 0. One
method involves the complete neglect of differential overlap (LE-CNDO), the other uses
intermediate neglect of differential overlap (LUC-INDO). The determination of parameter
sets for the elements is discussed.

1. Introduction
The theory of point defects in solids has become very sophisticated and is capable of
making accurate predictions, and models of the solid as a large cluster of atoms have
been widely used (see for example Coulson et a1 1958, Messmer and Watkins 1970, 1973,
Larkins 1971, Hayns 1972, Hayns and Dissado 1975). A major problem with such
models is that for any practical size of cluster most of the atoms are surface atoms; the
translational symmetry of the crystal is ignored and atoms which are equivalent in the
bulk may not be equivalent in the cluster. The surface effects may be large: for covalent
materials some way of saturating dangling bonds is needed and for ionic materials the
long-range Coulomb effects should be included. For free-electron metals results have to
be checked carefully to see whether or not surface states are important.
The alternative to a special treatment of surface atoms is to impose some form of
periodic boundary condition on the cluster. This was done by Bennett et a1 (1971) in
their studies of adsorbates on a graphite substrate, where edge effects were removed by
replacing weak interactions between pairs of atoms within the cluster with interactions
with nearer neighbours outside the cluster. This was described as the imposition of a
‘periodic connectivity condition’.
This paper describes a formalism based on work by Dobrotvorskii and Evarestov
(1974) which incorporates the lattice translational symmetry in a way which allows
crystal properties at special points of the Brillouin zone to be calculated using a self-
consistent scheme without the need for k vector sampling. The method is made compu-
tationally feasible by the use of well-established semiempirical techniques. In the two
following papers, the method is applied to covalent crystals, namely diamond and
silicon, and to ionic crystals (Harker and Larkins 1979a, b, hereafter referred to as papers
I and I1 respectively). The aim of this series of papers is to show that a relatively simple
t Permanent Address: Department of Chemistry, Monash University. Clayton 3 168, Victoria, Australia.

0022-3719/79/132487 + 09 $01.00 0 1979 The Institute of Physics 2487

2488 A H Harker and F P Larkins

theory is capable of very accurate predictions of the properties of perfect solids. The
same theory is equally valid for solids with defects, and the semiempirical parameters
obtained may be used in cluster calculations without translational symmetry in the
knowledge that they are specially suited to solid state problems.

2. Theory

The method described below is based on the linear combination of atomic orbitals
(LCAO) or tight-binding model of solids. The calculations are simplified in two ways.
First, the Hamiltonian matrix elements are simplified by using the semiempirical all-
valence molecular orbital approximations described by Pople and Segal (1966). By
neglecting some integrals and replacing others by approximate values based on a set of
numerical parameters, the calculation can be performed much more rapidly, although
it is kept self-consistent. These approximations may be made at two levels: the complete
neglect of differential overlap (cmo) is introduced in 4 2.2 and expressions with inter-
mediate neglect of differential overlap (INDO) are given in 42.4. The second major
simplification, described in 4 2.3, is the large unit cell (LUC) theory described by
Dobrotvorskii and Evarestov (1974) and Evarestov et a1 (1975); the large unit cell gives
a reduced Brillouin zone onto which the k vectors of the normal zone are mapped. This
reduces the number of reciprocal space points which need to be considered.

2.1. Tight-binding method

To establish notation, consider a microcrystal of N 3 large unit cells each containing n'
spin orbitals. The total number of electrons in the system is JV = n'N3. With the use of
a closed-shell Hartree-Fock approximation, the total electronic wavefunction (D is
represented as a single determinant of order JV:
(D(1... M ) = d [ $ , ( k , v). . . $&k, v ) . . . $,(k, Y)]. (2.1)
Within the independent-particle model, the optimum crystal orbitals $,(k, v) for a
chosen basis set are to be determined self-consistently. k denotes a wavevector and v a
position vector. In constructing the one-electron crystal orbitals and in solving the
Hartree-Fock equations the following facts are used:
(i) The translational symmetry of the crystal yields the Bloch condition
$$, v + R,,) = exp(ik - RJ $,(k Y) (2.2)
where R,, is the position vector defined as R,, = plui + p2ai + ,u2 U'3 ; Pl, P2, P 3 are
integers and a : , ai and U : are the translation vectors for the LUC that are characteristic
of the crystal symmetry. The translational symmetry ensures that the electron density
for the crystal has the periodicity of the lattice.
(ii) A periodically repeated LUC microcrystal, defined using Born-Von Karman
cyclic boundary conditions, requires the wavefunction to be repeated after N cells, i.e.

$& l" + N ) = $& 4. (2.3)

The cyclic boundary conditions imposed determine the allowed values for k. For a
microcrystal containing N 3 lattice points the domain in k space will be spanned by N 3
reduced lattice vectors.
 LVC .semiempirical M O approach to properties of solids I 2489

(iii) The crystal or Bloch orbital $,(k, Y) is approximated by a linear combination of

one-electron molecular orbitals X,(k, Y - R,,) in the cells. Hence

Because of the translational symmetry of the molecular orbitals, the solution in one cell
of the crystal enables the complete crystal orbital to be specified. Furthermore, the
one-electron molecular orbitals may be expressed as a linear combination of basis
functions 4p chosen to represent the atomic orbitals in each cell:

Hence, the one-electron crystal orbital is expressed as

The basis functions may be chosen in the same manner as for molecular systems.
The problem is therefore reduced to the determination of the coefficients cp,(k) for one
large unit cell.
The total Hamiltonian for the microcrystal consisting of N (= n'N3) electrons may
be written in atomic units as

where the summations are over all the electrons and the nuclei of the system and the
terms have their standard meaning. The Hamiltonian possesses the translational
symmetry of the lattice (Lowdin 1962).If the standard closed-shell Hartree-Fock theory
in the LCAO approximation (Roothaan 1951) is followed and the translational symmetry
of the crystal and the cyclic boundary conditions are used, the Hartree-Fock secular
equation can be split into N 3 independent parts. Each part corresponds to a specific
point k in the space of the reduced wavevector (Lowdin 1962, Del Re et al 1967, Andre
1969).
The Hartree-Fock equations for the microcrystal corresponding to a specific wave-
vector k become
c (Fpq(k)
P
- E,(k) S,,(k)) cp,(k) = 0. (2.8)

The summation is over the basis functions for a single LUC and the Fock and overlap
matrices are defined as follows:

(2.9)

(2.10)
with

El3
2490 A H Harker and F P Larkins

and
sop,Pq
= (4,P -Ro)14q(Y - RJ). (2.12)
The summation in equations (2.9)and (2.10) is over all the large unit cells ,U of the micro-
crystal and the central cell is denoted by Ro. As for molecules, the Fock matrix elements
may be expressed in terms of one- and two-electron components:
(2.13)

(2.14)
and
all allbasis

(2.15)

(2.10)

(2.17)

(2.18)

The summation is over all the molecular orbitals which would be doubly occupied by
the n’ electrons from one cell; this corresponds to n‘/2 energy bands. In principle k is
summed over all the allowed values of k, which is N 3 when there are N 3 cells in the
microcrystal. This corresponds to summing over all the occupied states of the micro-
crystal.

2.2. Semiempirical approximations: CNDO

The first stage in the reduction of the secular equation (2.8) to a manageable form is to
simplify the Fock matrix elements Fop,p4. The most promising approach, which includes
the most important interactions and uses a self-consistent procedure, is through one of
the family of zero differential overlap techniques (Pople and Beveridge 1970). Similar
methods have been used before on periodic structures, in particular on infinite polymers
(Morakuma 1971, Beveridge et a1 1972).
The main features of the complete neglect of differential overlap (cmo) and inter-
mediate neglect of differential overlap (INDO) approaches are as follows. A valence-
electron approximation is adopted, which implies that only the valence electrons are in
 LUC semiempiricalicro approach to properties of solids I 249 1

the bonding region and are polarised by the presence of neighbouring atoms. The
valence atomic orbitals are represented by a minimal Slater basis set. In CNDO theory
overlap integrals are neglected, i.e.

SOP,P4 = 'OlI'P4
(2.19)
and the condition
(6;6:16:4:) = 'Op'pq'v??rsYTB (2.20)
is applied, so that all three- and four-centre integrals and many of the one- and two-
centre ones are eliminated. Here A and B are the atomic species on which orbitals p and
r are based. In our work the Coulomb integrals yg
are evaluated directly using s-type
Slater functions. These modifications result in a considerable reduction in the com-
plexity of the Fock matrix and the secular determinant. The problem is further simplified
by the use of empirical data to parameterise the remaining integrals. The off-diagonal
core Hamiltonian matrix elements are approximated by
HOp,pq = PiB'Op,pq (2.21)
where is known as a resonance integral and is defined by
PiB = +KA,(BA + PB). (2.22)
It is dependent only on the nature of the atoms A and B and not on the orbital type.
K , is a constant usually set equal to unity. The diagonal core Hamiltonian elements
have the form
Hop,oq = 2 P + A,") + +
-qzA YE- 1 z B y z (2.23)
8. v

where the summation is over all atoms B and all cells v of the solid. Zp"and A t are the
ionisation potential and electron affinity respectively for the pth orbital on atom A and
z is the core charge, equal to the number of valence electrons. From equations (2.15)
and (2.20)
'Op, Op = 1
r. v
- +P;i?z (2.24)

and
P - 'Pop?%
G O p , P= 2 P4 (OP * P4). (2.25)

The Fock matrix elements from equation (2.9) have the following form within the
CNDO formalism :
Fpp(k) = - +('," + A:) + $YE - 'BYZ + u1 PiBSOp, vp exp(ik Ry)
B, v +o

(2.26)

and
Fpq(k) = 1
V
PiB'Op, vq exp(ik' R v ) - 4 1 v k'
:7
' ~ q ( ~ ' ) exp[i(k + k') * Rvl' (2.27)

Equation (2.26) differs from equation (11) of the work by Evarestov and Lovchikov
(1977) in that the third term in the above equation has been inadvertently omitted in
their published work. Furthermore, the density matrix terms involve the variable k and
2492 A H Harker and F P Larkins

a summation over k' has been omitted in the fifth term of the earlier work. Equation
(2.27) is in agreement with equation (12) of the previous work.

2.3. Large unit cell method

In the large unit cell method described by Dobrotvorskii and Evarestov (1974) the shape
and size of the cells are chosen carefully so that symmetry points of interest in the
Brillouin zone at k become equivalent to the r' point (k' = 0) in the reduced zone
(Evarestov et a1 1975, Petrashen et a2 1975). The method has been compared with the
small periodic cluster approach (Zunger 1974) by Evarestov et a1 (1976). Only the point
k = 0 is considered in the calculation and the reciprocal-space sums in equation (2.17)
are reduced to just the point k' = 0. This allows selected properties of the crystal to be
calculated on the basis of data for the special points alone (Chadi and Cohen 1973).
The secular equations to be solved have the form
c (FP,(0)
P
- Ez(0)) C p z ( O ) = 0 (2.28)

with
FPP(0)= - -(I
2 P
A + At)+ $-
B
(PB(o) - 'B) ??B + vp - ' 0 ~ )

-i
1 Ppp(0)~,(2 (2.29)

where in principle the summation v is over all cells and the summation R is over all
atoms in the large unit cell. Also PB(0)= Er Prr(0),where the atomic orbital r is on
atom R:
FpAq,(0) = P i B C Sop, vq - $ Pp,(O) c YE. (2.30)

Equations (2.29) and (2.30) are equivalent to equations (14) and (15) respectively given
by Evarestov and Lovchikov (1977).

2.4. The INDO upproximation

An alternative, less extreme semiempirical method is the intermediate neglect of differ-
ential overlap (INDO) method. The one-centre two-electron repulsion integrals are
retained, along with the distinction between orbital types. Hence, the Fock matrix
elements within the LUC-INDO method have the following form:

(2.31)

(2.32)

(2.33)
for p and q on the same atomic centre.
 LUC semiempirical M O approach to properties of solids I 2493

Uop:o p is essentially the energy of an electron in atomic orbital + p in the electrostatic

field of its own core and the inner-shell electrons. The other terms have the same meaning
as before. Calculations for molecules suggest that the INDO method may be superior to
the cmo method, especially when open-shell systems are being considered (Pople and
Reveridge 1970).

3. Implementation of the LUC-CNDO method

The LUC-CNDQ method has been made a part of the Harwell computer program MOSES
(Molecular Orbital Semi-Empirical System). The integrals between atomic orbitals are
evaluated using the standard CNDO approximations and depend only on the atomic
parameters <, (orbital exponent), the electronegativity $1; +
A:) and the bonding
parameter Pg. The Coulomb integrals yz are calculated using s-type orbitals, not from
the empirical expression given by Ohno (1964), which was used by Evarestov and
Lovchikov (1977).
There are three basic types of lattice sums which occur in the problem: the sum of
Coulomb integrals C, yTB, the sum of overlap integrals, C, Sop,- and the Madelung-
type sum CB(PB(0) - zB)2, yg.
Although the summation may in principle be over all
the LUC of the microcrystal, it seems from our calculations within the cmo method that
a limit must be placed on the lattice sums if meaningful results are to be obtained.
Specifically, the Fock matrix elements must not include summations over more than
one shell of atoms. That is, only one I Ryl value may be included for each matrix element.
This point is discussed more fully in paper 11. It follows that a critical cut-off distance
Rcritcan be determined for a chosen LUC and this limits the interatomic interactions
which may be included. In general, Rcritincreases with the size of the large unit cell.
The total energy for the system is given by the relationship
(3.1)

where the summation A includes all atoms in the LUC,while the summations I3 and v
include all atoms within the chosen cut-off distance.
For ionic crystals, as described by Hayns (1972), Hayns and Dissado (1975) and
Itoh et a1 (1977), a long-range residual Madelung term is included in the diagonal Fock
matrix elements (equation 2.29) with a corresponding modification of the total energy
for the system. Applications to ionic crystals are discussed in 111.
Where open-shell systems are discussed in papers I1 and 111, a scheme based upon
the theory of Slater et al (1969) for orbitals with non-integral occupation numbers is
used. This 'pseudo closed-shell' scheme was incorporated into the MOSES program by
J H Wood (1975, unpublished data).

4. Choice of parameter set

CNDO and any other semiempirical method stands or falls by its parameter set, so it is
important to have a systematic way of choosing the parameters. It is not reasonable to
expect a theory with such a restricted set of parameters to give perfect values for all the
physical observables; some degree of compromise is necessary.
The standard CNDO parameters were fixed by fitting to Hartree-Fock calculations
2494 A H Harker and F P Larkins

on small molecules. As experimental results are to be reproduced, it is more logical to

fit to'experimental quantities, although Hartree-Fock work gives useful starting values
for the exponents (,. This philosophy of fitting to experiment is basic to the work
described by Ringham et al (1975 and references therein) and was used successfully by
Mainwood and Stoneham (1976).
The aim of the present work is to derive parameters appropriate to the solid state,
but those parameters will not necessarily be suitable for molecular calculations.
Diatomic metal molecules, for example, can have very different interatomic spacings
from the solid and may well need different parameter sets. Similarly, parameters derived
from non-polar systems will almost certainly not perform well in ionic calculations.
Papers I1 and I11 show two different schemes for choosing the parameters. For
carbon and silicon the aim was to obtain good agreement with the best calculated band
structures for the solids. The LUC method allows the orderings of levels of different
symmetries to be checked and those orderings put some bounds on the parameter set.
Thus, starting from standard CNDO values, it is fairly easy to get accurate agreement
from this few-parameter model: this in itself shows that most of the important physical
effects are included in the theory. Diamond and silicon are discussed in paper 11.
For the MX ionic crystals of paper 111, the parameters are chosen by using CNDO
calculations on the small molecules M,, MX and X, (Mainwood 1970, Itoh et al 1977,
Jain 1977) and experimental bond lengths, dissociation energies and dipole moments
are fitted. The important point is that for MX the dipole moment depends mainly on
the electronegativities of the metal and halogen and the bond length is determined
mainly by the orbital exponents. The procedure is then to take standard electronegativi-
ties, fit [, and <, to the equilibrium bond lengths of M, and X, and adjust j?, and Px
to get the right dissociation energies. The electronegativities are then adjusted to fit the
MX dipole moment. Some iteration is necessary to obtain a good set of final parameters
and there may not be a unique choice. Again, the accuracy of the results for solids says
much for the method, as shown in paper 111.

Acknowledgments

We thank Dr A M Stoneham for his encouragement and for stimulating discussions.

One of us (FPL) thanks Harwell for the hospitality extended to him while on study
leave from Monash University.

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 LUC semiempirical M o approach to properties of solids I 2495

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