Covalent Bonding

1
POTENTIALS FOR COVALENT SOLIDS SEMICONDUCTORS

The covalent bonding between atoms arises naturally in complete quantum
mechanical treatments of the cohesion, such as calculations based on the density
functional theory (DFT) where the covalent bonding is treated practically exactly.
However, as in many other cases, use of these methods in studies of complex structures
of defects may not be feasible.
Hierarchically, the next possible step is the tight-binding approximation which
accounts for the electronic structure of the system but without self-consistent evaluation
of the relevant Hamiltonian. Rather, the Hamiltonian is fixed and parameters in it are
fitted empirically. The first such study was made by Chadi 1. This approach captures
the following quantum mechanical features of bonding:
The energy of a system does not depend only on the separation of atoms but also
on the angles between chemical type bonds formed between pairs of atoms.
Hence, forces acting on atoms also depend on angles between bonds.
Diamond type structure of silicon

Covalent bonds
connecting lines
are
marked
by
Dark atoms and bonds show the

tetrahedron with 109.7o angles of
bonds
However, even tight-binding calculations are frequently very extensive and time
consuming. For this reason, empirical potentials of bonding in covalent solids have
been developed that incorporate the most important features of the directional character
of bonding in these materials. We review here briefly Stillinger-Weber potential and
Tersoffs potential, originally developed for silicon but generalized to other covalent
materials2. The most important characteristic that has to be reproduced by all such
potentials is preference for tetrahedral configurations of atoms and related diamond
crystal structure.
1
D. J. Chadi, 1979, Phys. Rev. B19, 2074; 1984, Phys. Rev. B29, 785
2 F. Stillinger and T. Weber, 1985, Phys. Rev. B 31, 5262; J. Tersoff, 1988, Phys. Rev. B 37,
6991; 38, 9902
Stillinger-Weber potential
The potential energy of a system of N interacting particles can be generally written
as
E p = ! V2 (i, j) +! V3 (i, j, k) + ! V4 (i, j, k, !)+ ....

i, j
i, j,k
(S1)
i, j,k,!
where V2 describes the two-body (pair) interactions, V3 three-body interactions, V4

four-body interactions etc. In the scheme proposed by Stillinger and Weber only twoand three-body interactions are included.
The two-body interactions are described by a pair potential such that
V2 (i, j) = ! "2 (rij / # )
(S2.1)
where the functional form
!2 (r ) = A(Br "p " r "q )exp[(r " a)"1 ] for r < a
(S2.2)
!2 (r ) = 0 for r # a
1/6
is set such that the depth of 2 is 1 and is chosen such that d!2 (r = 2 ) dr = 0 .
A, B, p, q and a are all positive adjustable parameters (Note: a is not a lattice
parameter). This form automatically cuts-off the potential and all its derivatives at r =
a; note that for r < a !2 (r ) is negative and as r ! a (r ! a)!1 " !# and therefore
exp[(r ! a)!1 ] " 0 .

The three-body interactions are described such that
where
V3 (i, j, k) = ! "3 (rij , rik , rjk )
(S3.1)
! 3 (rij ,rik ,r jk ) = h(rij , rik ," jik ) + h(r ji , rjk ," ijk ) + h(r ki ,rkj ," ikj )
(S3.2)
! jik is the angle between vectors rij and rik and

h(rij , rik , ! jik ) = "exp[#(rij $ a)$1 + #(rik $ a)$1 ](cos! jik +
h(rij , rik , ! jik ) = 0 for rij , rik > a
) for rij , rik < a
1 2
3
(S3.3)
and are positive adjustable parameters. For the ideal tetrahedral angle ! T = 109.47
cos(! T ) = "1/ 3 and h = 0.

2
3
The seven parameters A, B, p, q, a, and are all fitted to assure that the diamond
structure is the lowest energy structure and the melting temperature is in a reasonable
agreement with experiment. For silicon the most satisfactory parameters were found to
be:
A = 7.049556277, B = 0.6022245584, p = 4,
q = 0, a = 1.80, = 21.0
= 1.20
Figure 1a shows the corresponding binding energy per atom of Si (in reduced units)
versus number density (in reduced units) for several simple structures: f.c.c, b.c.c.,
simple cubic (s.c.) and diamond. In order to obtain correct lattice spacing and cohesive
energy of the diamond structure the parameters and have to be chosen as =
209.51nm = -50 kcal/mol. Figure 1b shows the corresponding binding energy per
atom of Si calculated using a DFT based method. (Note that in Fig. 1a the x axis is
density and in Fig. 1b volume and these two quantities are related inversely).
The Stillinger-Weber potential does assure that the diamond structure is the lowest
energy structure but agreement with the DFT calculations is only tentative but the order
of energies for different structures is reasonable.
(a)
(b)
Fig. 1. (a) Energy versus density dependencies for diamond, fcc, bcc and simple cubic
(sc) structures of silicon calculated using the Stillinger-Weber potential. (b) Energy
versus volume dependencies for diamond, fcc, bcc and simple cubic (sc) structures of
silicon calculated using a DFT method3.
3 M.
T. Yin and M. L. Cohen, 1982, Phys. Rev. B 26, 5668; 1984, Phys. Rev. B 29, 6996
Tersoff potential
The most appropriate empirical schemes for covalently bonded solids are those
which reflect correctly the angular dependence of atomic interactions that is a
consequence of the quantum mechanical nature of bonding. One of the most successful
empirical schemes of this type is Tersoff's potential, originally developed for silicon. It
is based on the concept of bond-order that is a measure of the variation of the strength
of a bond between two atoms with the surrounding atomic environment, in particular,
the coordination number. Within this scheme the total energy is decomposed into two
parts
(S4)
E p = U rep + U bond
The first term is the short-range Pauli repulsion and the second term the bonding term.
The repulsion is represented by a pair potential, ! , so that
U rep =
1
2
# ! (rij )
(S5)
i" j
where rij is the separation between atoms i and j. In the Tersoff's scheme the pair
potential is written as
!(rij ) = A fcut (r ij ) exp("# 1 rij )
(S6.1)
where
#1, rij < R ! D

%%
fcut (rij ) = $12 ! 12 sin "2 (rij ! R ) D ,
%
%&0, rij > R + D
R ! D < rij < R + D
(S6.2)
is a cut-off function that limits the range of the interactions to the first nearest neighbor
shells in the diamond lattice and A, ! 1 , R and D are constants determined within the
empirical fitting.
The bonding term is proportional to the bond-orders, bij , relating to the covalent bonds
formed between atoms i and j, and is written as
U bond = =
where
1
2
" b ij FA (rij )
(S7.1)
i! j
FA (rij ) = ! B fcut (rij ) exp(!" 2 rij )
(S7.2)
is a rapidly decreasing function of the separations rij and B and ! 2 are again adjustable
parameters. The bond-order, b ij , represents the many-body, non-central character of
atomic interactions and is taken as a monotonically decreasing function of the
4
5
coordinations of atoms i and j. In the latest version of the Tersoff's potentials b ij has
the following form
b ij = 1 + p n ! nij
where
! ij =
k " i,j
"1 2n
(S8.1)
fcut (r ik ) exp[$ 33 (rij % rik ) 3 ] g(& ijk )
(S8.2)
The summation extends over all the neighbors k of the atoms i and j; p, n and ! 3 are
adjustable parameters and g(!ijk ) is a function of the angle ! ijk between the i-j and i-k
bonds. This function has been parameterized as
g(! ijk ) = 1 + c 2 d 2 " c 2 d 2 + (h " cos ! ijk ) 2
(S8.3)
where c, d, and h are empirically fitted constants.

The parameters figuring in the Tersoffs potential were determined by fitting the
cohesive energy, lattice spacing and bulk modulus of silicon in the diamond lattice and
the volume dependence of the energy of several other structures (hcp, bcc, -tin etc.)
predicted from first-principles pseudopotential calculations3. These dependencies are
shown in Fig. 2. All the fitting parameters involved in the Tersoff's potential for silicon
are summarized in the table shown below.
A (eV)
1.8308 x 10
1.0039 x 10
B (eV)
4.7118 x 10
1.6218 x 10
! 1 ()
2.4799
-5.9826 x 10
! 2 (-1)
1.7322
! 3 (-1)
1.7322
!6
1.0999 x 10
7.8734 x 10
!1
R ()
2.85
D ()
0.15
5
1
!1
An analogous potential was developed by Brenner4 for carbon and hydrocarbons.

It was used, for example in molecular dynamics calculations of chemical vapor
deposition of diamond films.
4 D.
W. Brenner, 1990, Phys. Rev. B 242, 9458.
(a)
(b)
Fig. 2 Comparison of energy versus volume dependencies for diamond, fcc, bcc and
simple cubic (sc), simple hexagonal (sh) and -tin structures of silicon calculated using:
(a) DFT based pseudopotential method3; (b) Tersoff potential.
6
In electronic structure calculations based on the density functional theory (DFT) the
interesting finding is that at the compression at which the volume per atom decreases by
about 16-17%, i.e. when the volume per atom becomes about 16.53, the diamond
structure starts to have a higher energy than the structure corresponding to tin (see
Fig. 2a).
Hence calculations predict that at this compression there is a phase
transformation from the diamond to the tin structure. This transformation was,
indeed, observed experimentally. The interesting feature of the Tersoff potential is that
it reproduces this aspect of silicon quite well, as seen from Fig. 2b.

Covalent Bonding

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1

POTENTIALS FOR COVALENT SOLIDS SEMICONDUCTORS

Diamond type structure of silicon

Dark atoms and bonds show the

E p = ! V2 (i, j) +! V3 (i, j, k) + ! V4 (i, j, k, !)+ ....

where V2 describes the two-body (pair) interactions, V3 three-body interactions, V4

V2 (i, j) = ! "2 (rij / # )

where the functional form

!2 (r ) = A(Br "p " r "q )exp[(r " a)"1 ] for r < a

exp[(r ! a)!1 ] " 0 .

V3 (i, j, k) = ! "3 (rij , rik , rjk )

! jik is the angle between vectors rij and rik and

) for rij , rik < a

cos(! T ) = "1/ 3 and h = 0.

#1, rij < R ! D

R ! D < rij < R + D

FA (rij ) = ! B fcut (rij ) exp(!" 2 rij )

fcut (r ik ) exp[$ 33 (rij % rik ) 3 ] g(& ijk )

g(! ijk ) = 1 + c 2 d 2 " c 2 d 2 + (h " cos ! ijk ) 2

where c, d, and h are empirically fitted constants.

An analogous potential was developed by Brenner4 for carbon and hydrocarbons.

W. Brenner, 1990, Phys. Rev. B 242, 9458.

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