LENNARD-JONES POTENTIAL

Assuming that the total energy is determined solely by pair interactions between the
atoms we have
1
E p = # !(rij )
2 i, j
i" j

where !(rij ) is a pair potential. A simple potential of this type is the Lennard-Jones
(L-J) potential (J. E. Lennard-Jones, Proc. Roy. Soc. A106, 463, 1924) which was
originally suggested to describe interaction between atoms of inert gasses,
specifically argon. The general form of this potential is:

!(r ) =

"n
rn

"m
rm

where ! n and ! m are constants fitted to some physical properties.

In inert gasses the interaction is Van der Waals type that arises from the dipole-dipole
interactions. The attractive part of such interaction corresponds to m=6. The most
common form of the Lennard-Jones potential is the so-called (6-12) form

+ $ # ' 12 $ # ' 6 .
!(r ) = 4" - & ) * & ) 0
% r( 0
-, % r (
/
This is the potential that will be used throughout all the assignments. At this point
the range of interactions is not limited but, obviously, lim #(r) = 0
r! "

The minimum of (r) is determined from the condition

12
6
d! 24" + % $ (
% $( .
- #2
=
+' * 0=0
dr
r - '& r *)
& r) 0
,
/
6
which gives rmin = 2 ! . Inserting this value into the potential yields !min = "# .
These two relations determine the meaning of parameters and which is shown in
the Figure below.

Lennard-Jones potential without cut-off.

The two parameters, and , can be fitted to experimental data such as the
equilibrium bond length (lattice parameter at equilibrium), equilibrium bond energy
(cohesive energy) or, alternatively, the bulk modulus at equilibrium.
Fitting for face-centered-cubic argon gives
= 3.405

= 0.010323eV

! / k B = 119.8K

where k B is the Boltzmann constant.

The mass of the argon atom is 6.68 x10-23 g. For the three-dimensional case the
melting temperature, found by a molecular dynamics study, is Tm = 83.9K.
However, for the two-dimensional case, which will be investigated in assignments,
the melting temperature will be lower.

Potential cut-off
In calculations we obviously have to limit the range of the potential. However, this
should be done by allowing the potential to converge smoothly to zero at a chosen
cut-off radius, rcut . By smoothly we mean that not only the function but also its
derivative (and possibly even second derivative) converge to zero at rcut . If the cutoff leads to an abrupt change in the potential and its derivative it could lead to
unphysical problems when minimizing the energy and/or when solving the equations
of motion.
In order to implement a smooth cut-off we choose a separation ro , somewhat smaller
than rcut , and for ro < r < rcut replace the original potential by a 'tail' !(r) such that

!(ro ) = "(ro ) and ! # (ro ) = "# (ro ) joins smoothly !(r ) at ro . At the cut-off radius,
rcut , we impose that !(rcut ) = ! " (rcut ) = 0 . This leads to a 'smooth' termination of the
potential. A possible form of such tail is the polynomial:
3
2
!(r) = A(r " rcut ) + B(r " rcut ) for which !(rcut ) = ! " (rcut ) = 0 .

Coefficients
A
and
B
then
!(ro ) = "(ro ) and ! # (ro ) = "# (ro ) .
In the following we choose rcut

have

to

be

chosen

= 7.5 and ro = 7.0.

such

that

The condition

!(ro ) = "(ro ) and ! # (ro ) = "# (ro ) gives::

A = 6.8102128x10-3 eV/3

B = 5.5640876x10-3 eV/3

Lennard-Jones potential with

the cut-off