PAIR POTENTIALS

Purely repulsive potentials

Hard spheres at constant volume
The simplest possible pair potential is the hard sphere potential defined as:

$ " for r # ro
!(r) = %
& 0 for r > ro

(EP1)

This means no interaction for separations r > ro and infinite repulsion for r ! ro (see
Figure 1a).

! (r)

! (r)

r0
(a)

"#

r0

r1

(b)

Fig. 1. (a) Hard sphere potential. (b) Hard sphere potential with an attractive well.
This potential is often used, without proper mathematical definition, to represent
crystal structures assuming a fixed volume per atom. However, only close-packed
structures, such as face-centered cubic and close-packed hexagonal are stable within
the hard sphere model. When used for other structures one needs some sticks or
glue to hold the structure together, which means that purely repulsive interactions
are insufficient even at fixed volume. An attractive well can be added as shown in
Fig. 1b for the range of separations r0 < r < r1.
A number of pair-potentials were constructed to describe only repulsive interaction
for small separations of atoms. The purpose of these potentials is two-fold. First,

they have been used in studies of atomic collisions in which the attractive part of the
atomic interactions plays only a minor role. Secondly, they can represent the shortrange atomic interactions in the schemes where the attractive part is described by
other means such as another pair potential, tight-binding method, embedding function
etc. Most common potentials of this type are the Born-Mayer potential and its
modifications and screened Coulomb potentials.
Born-Mayer potential
This potential was originally introduced to represent the closed shell repulsion
between ions in ionic crystals (M. Born and J, E, Mayer, Z. Phys. 75, 1, 1932) but it
has been used in many other cases, simply when a strong repulsion at short
separations is described by an uncomplicated analytical function. The form of this
potential is
(EP2.1)
!(r) = Ae"Br
where A and B are two adjustable parameters. This potential was modified by
Huntington (H. B. Huntington, Phys. Rev. 91, 1092 1953) by introducing into it the
nearest-neighbor separation r0 :
"B(r"r 0 )/r 0
(EP2.2)
!(r) = Ae
In the case A is the value of the potential at the first nearest neighbors separation.
Screened Coulomb potentials
These potentials are most appropriate for metals where the electrons screen very
effectively the Coulomb charges of the ions and thus the corresponding Coulomb
interactions. In general, screened Coulomb potentials have the form

Z1Z2
"(r a s )
(EP3)
r
where Z 1 and Z 2 are the ionic charges of the two atoms and ! is a screening
function; a s is the corresponding screening radius beyond which the interaction is
very weak.
The simplest form of the screening function was proposed by Bohr (N. Bohr, Kgl.
Dansk. Vid. Selsk. Mat.-Fys. Medd. 18, No.8 1948) as ! = exp(" r a s ) . The
screening function can be determined on the basis of the Thomas-Fermi model in
which the screening of a charge by the free electrons gas is considered. In this model
! can only be found numerically but a good approximation is
!(r) =

!TF =

1
8k
2
exp(# k TF r) where k TF = F
4"
"

(EP4)

and k F is the Fermi vector; the units are defined such that with e 2 4 !" 0 =1,
! = m = 1; the lengths are then in atomic units (5.29x10-11m) and energy in Hartrees
= 2Ry (4.36x10-18J).

Potentials with repulsive and attractive parts

Modified hard spheres potential
A modification of the hard sphere potential, which allows for an attractive part of the
potential, is the square well potential (see Figure 1b) defined as
' " for r # ro
)
(EP5)
!(r) = ( $% for ro < r < r1
) 0 for r & r
*
1
However, based on studies of the interaction of atoms forming diatomic molecules
(dimmers), a more realistic assumption is that the potential varies smoothly from
strongly repulsive at short separations of atoms to attractive at intermediate
separations and converging to zero for large separations, as shown in Fig. 2.
Morse potential
This potential, originally proposed for dimmer molecules (P. M. Morse, Phys. Rev.
34, 57, 1929) has the functional form

!(r) = De "2#(r"r0 ) " 2De "#(r"r 0 )

(EP6)

and its shape is shown in Fig. 2. When r = 0 ! = De" r0 (e "r0 # 2) which can be
very large provided

e !r0

>> 2 . For r ! " ! " 0 and the potential has a minimum

equal to -D for r = r0 .
! (r)

Fig. 2. Pair potential of Morse type with attractive and repulsive part

This form of the pair potential has often been used not only for molecules but also to
describe atomic interactions in solids. The parameters D, and ro can be determined
by fitting, for example, the cohesive energy at equilibrium, using equation (G20 with
U = 0, i. e. E p =

1
# !(rij ) ), equilibrium lattice parameter from the conditions of
2 i, j
i" j

equilibrium ! "# = 0 ( ! "# given by equation G23 with U = 0 and also zero velocities
of the particles), and the bulk modulus given by equation (AG6). Such fitting was
performed, for example, by Girifalco and Weizer (Phys. Rev. 114, 1123, 1959) for a
number of FCC and BCC metals. However, they found that the stability of the lattice
is very sensitive to the cut-off of the potential.
It should be noted that this potential, originally developed for molecules, has no
physical justification for solids other than that it reflects the fact that there must be
repulsive and attractive parts of the interaction and these are joined smoothly.
Lennard-Jones potential
Lennard-Jones potential (J. E. Lennard-Jones, Proc. Roy. Soc. A106, 463, 1924) has
the general form
"
"
!(r) = nn # mm
(EP7.1)
r
r
It was originally derived for inert gasses, in particular argon, the cohesion of which is
due to the Van der Waals forces arising from the dipole interaction. The attractive
part corresponds in this case to m=6 and the most common form of this potential is
the so-called (6-12) form

+ $ # ' 12 $ # ' 6 .
!(r) = 4" - & ) * & ) 0
% r ( 0/
-, % r (

(EP7.2)

where corresponds to this value of r for which = 0 and the minimum value of the
potential is ! min = "# at rmin = 6 2 ! .
Buckingham potential
The general form of this potential is

C
(EP8)
r6
where A, B and C are adjustable parameters. The first term is the (Pauli) repulsion of
ions at short separations described by the Born-Mayer potential. The second term
!(r) = A exp ("Br ) "

describes attraction that can have various physical origins, for example Van der
Waals attraction.
Short range purely empirical pair potentials
Empirical pair potentials of the type similar to the Morse potential shown in Fig. 2
but cut at a cut-off radius, rcut , were constructed for many elements. The usual
requirement is that the potential is cut-off smoothly, i. e. at least
!(rcut ) = d!(r) dr
= 0 is imposed; zero second derivative is required if lattice
r=r
cut

vibrations are to be studied. These potentials are usually short range: Most
commonly for BCC metals rcut lies between the second and third neighbors and for
the FCC metals between third and fourth neighbors. One of the most successful
potentials of this type has been the Johnson's potential (R. A. Johnson, Phys. Rev.
134, 1329, 1964) described analytically by three smoothly spliced polynomials of the
form
(EP9)
A(r ! B)3 + Cr + D
This potential was constructed for several bcc metals by fitting the lattice parameter
at equilibrium and partly elastic moduli but the Cauchy relation C12 = C44 (cubic
system) is imposed if the energy of the system is represented by the pair potential
only.
! (r)

Short-range cut-off

Fig. 3. Johnsons potential

For metals it is more appropriate to describe by the pair potential only the energy
changes associated with the variation of atomic configurations at constant average
density of the material but not the whole total energy of the system. Such potentials
were derived from first principles for sp-valent metals in the framework of weak
pseudopotentials (see below). The potential energy is then written as
5

E p = U(!) +

1
$ "(r ij )
2 i, j

(EP10)

i# j

where U is the density dependent part of the energy in which is the average density
of the material. This part of the energy is the major contribution to the cohesion.
Furthermore, may also be a function of the density . If the density dependence of
the pair potential is neglected this description of the potential energy is valid provided
the density of the material studied does not deviate substantially from the reference
density, usually the density of the ideal equilibrium lattice for which the potential was
constructed.
The physical meaning of the pair potential in equation (EP10) is entirely different
from that based on interaction of atoms in molecules. It describes an effective
interaction of atoms which form a medium of a given density composed of a large
number of these atoms. This potential does not describe interaction of isolated
pairs of atoms but it describes changes of the potential energy associated with
the changes of the configuration of the atoms at constant density.
Evaluation of stresses and elastic moduli for the case that a pair potential together
with a volume (density) dependent term represent the potential energy is summarized
in the section dealing with General aspects of atomistic computer modeling.
Pair potentials for s and p bonded metals: Justification for the empirical shortrange potentials
In this section we discuss materials with pure metallic bonding in which the electrons
are entirely delocalized, the Fermi surface is close to a sphere and the system is well
described in a nearly free-electron model. The following elemental metals belong to
this category: Li, K, Na, Rb, Cs; Be, Mg, Zn, Cd, Hg; Al, Ga, In, Tl; Sn, Pb; Ca, Sr,
Ba, as well as alloys formed from these elements, such as Li-Mg alloys.
In the materials listed above the potential, describing the interaction of electrons with
the nuclei or ions, is represented by a pseudopotential that can be regarded as a weak
perturbation when solving the Schrdinger. Such pseudopotential is defined as
follows:
(i) Core electrons are bonded together with the nucleus forming an ion of effective
positive charge, Z, which is equal in magnitude to the valence of the metal i. e.
to the number of conduction electrons that are not included into the core.

(ii) The true potential of the ion core is replaced by the pseudopotential which is
constructed such as to induce the same electron density outside the atomic core
as does the true atomic potential.
(iii) The pseudopotential is regarded as a weak perturbation for the conduction
electrons so that these can be treated as nearly free and standard perturbation
theory can be used to solve the Schrdinger equation.
The potential energy of the system can then be written as

Ep =

1
$ !(rij ,") + U(")
2 i, j

(EP11)

i# j

where the density dependent term U() is the zeroth and first order term in the
perturbation expansion of the energy and the pair potential is the second order term.
Examples of pair potentials for potassium, magnesium and aluminum, derived using
corresponding pseudopotentials, are shown in Figs. 4a-c.

Fig. 4a Pair potential for BCC potassium positions of 1st, 2nd and 3rd neighbors
are marked (a = 5.233). The minimum of the potential is about 0.03eV,
much smaller than the cohesive energy.

Fig. 4b Pair potential for HCP magnesium positions of 1st, 2nd and 3rd neighbors
are marked; a is the lattice parameter of the FCC lattice with the same
volume per atom (a = 4.518). The minimum of the potential is about
0.035eV, much smaller than the cohesive energy.

Fig. 4c Pair potential for FCC aluminum positions of 1st, 2nd, 3rd, 4th and 5th
neighbors are marked (a = 4.033). The minimum is at the second nearest
neighbors and the contribution is anti-cohesive (positive)
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Analytical expressions can be obtained in the limits of r ! 0 and r ! " . For small
values of r we obtain the screened Coulomb potential of the type (EP3)

Z 2 # a k 2TF
!(r,") =
exp(% k TF r)
4$r

(EP12)

where k TF is the Thomas-Fermi wave vector and ! a the volume per atom. The
density dependence of the potential is hidden not only in the direct dependence on
! a but also in the dependence of k TF on the density. For large values of r the
functional form of the pair potential is determined by the singularity of the effective
pseudopotential at q = 2k F which leads to the oscillatory behavior of the type
cos(2k F r)
(EP13)
!(r,") #
(2k F r) 3
This potential depends on the density via the density dependence of the Fermi vector
k F . The oscillations of the pair-potential are the typical Friedel oscillations the
nature of which is the same as oscillations of the density of the electron gas induced
by the presence of a positive charge that is screened by the electrons. Such potentials
may be relatively long range. Since the number of atoms at a distance r from an atom
2
is, for large values of r, proportional to r ; contribution of these atoms to the energy
cos(2k F r)
associated with the pair potential is !
and thus the convergence is very
(2k F r)
slow and only in the sense of the principal value (Cauchy sense). However, methods
of damping these oscillatory potentials have been developed.
Physical meaning of the pair potential for s and p bonded metals
The pair potential part of the energy, determined as the second order perturbation,
describes changes of the energy of the system associated with changing the
configuration of the atoms at constant density (i. e. constant total volume). The bulk
of the total potential energy is contained in U(!) that remains unchanged if the
configuration of atoms varies at constant volume of the system.
Hence, the physical meaning of the pair potential interaction described in this section
is for metals entirely different than pair potentials describing interaction of atoms in
molecules, pair potentials employed in ionic solids etc. Pair potentials entering the
potential energy given by equation (EP 11) describe an effective interaction of atoms
that form a medium of a given density composed of a large number of these atoms.
This type of pair potential is inapplicable when analyzing interaction of isolated
pairs of atoms.

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Deficiencies of pair potentials for metals

The volume dependent term, U, which represents the bulk of the cohesion, is a
function of the total volume, or average density, and cannot be easily defined locally.
This is the reason why most calculations employing pair-potentials have been
performed at constant volume when the contribution of this term is constant. This
precludes the use of this approach in situations where significant local variations of
the density exist. In lattice defects the local changes in the density are, of course,
common and the most extreme case are surfaces where the density sharply varies
away from the ideal crystal density a few atomic spacing below the surface to zero
after crossing the surface.
An exact solution of this problem can only be achieved by carrying out full quantum
mechanical calculations. However, a development which preserves the simplicity of
the description of the total energy on the level similar to equation (EP10) is the
embedded atom method and other many-body central force potentials schemes. In
these methods U(!) is replaced by an embedding function which depends on the
positions of atoms but it is not a simple pair potential.

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