ENERGY OF THE SYSTEM, FORCES AND STRESSES

Let us consider a system composed of N particles the positions of which are

determined by vectors ri (i = 1,...., N); the Cartesian components of these vectors will
be denoted as ri! where α = 1, 2, 3. If several distinct species of particles are
involved an indicator of the species has to be assigned to each particle.
The potential energy of this system, E p , is a function of the positions of the particles,
ri and here we assume we know how to calculate it. Hence

E p = E p (r1,r2 ,.....,rN ) (G1)

Commonly the system is translationally invariant1 and therefore

E p (r1 ,r2 ,.....,rN ) = E p (r1 + t, r2 + t,....., rN + t) ,

where t is a translation vector. Hence, E p may depend only on the relative positions
of the particles forming the system, i. e. on the vectors ri ! rj (i ≠ j = 1,2,...,N) that
we denote rij 2 and their components rij! v !i , where α = 1, 2, 3. In a given structure
there are relations between the vectors rij since when N of these vectors have been
chosen geometrical relations determine all the other vectors.
At finite temperatures particles are moving and their motion is characterized by their
velocities v i (i=1,2, ...., N); their components are marked v !i , where α = 1, 2, 3. The
Hamiltonian of such system of particles is
1 N
H = ! m iv2i + E p (r1,r2 ,.....,rN ) (G2)
2 i=1
where mi is the mass of the particle i. Assuming that the block of particles does not
N
move as a rigid body, so that !v i = 0 , the kinetic energy determines the temperature
i= 1
of the system in accordance with the equipartition theorem. In the three-dimensional
case 12 ! m i v 2i = Nk BT and in the two-dimensional case 12 ! m i v 2i = 2 2 Nk BT ; k B
i i
is the Boltzmann constant.

1 If there is an external force field interacting with the system studied such that the corresponding interaction energy
depends on the location of individual atoms and not only on their relative positions, this assumption is not valid.
2 It should be emphasized that this does not mean that E p is only a function of the separations of the atoms i and j
rij = ri ! rj . Of course, in the case of pair potentials, such as the Lennard-Jones potential, it is.
2

EQUATIONS OF MOTION
Classical equations of motion for the ith particle are
d 2 ri! !
mi 2 = Fi (! = 1,2,3) (G3)
dt
where Fi = !gradr (E p ) is the force acting on the particle i and its components are
i

#E p #E p
= "%
!
Fi = " (G4a)
#ri! k$ i #rik!
This can be re-written as
Fi! = # Fik! (G4b)
k "i
where
#E p
Fik! = " (G4c)
#rik!
can be interpreted as the α component of the force exerted on the particle i by the
particle k.

MECHANICAL EQUILIBRIUM
The necessary condition for the mechanical equilibrium is that the total force acting on
any particle of the system vanishes3, i. e.
Fi! = 0 for i = 1,...,N; ! = 1,2, 3 (G5)
The condition which guarantees that the equilibrium corresponds to a minimum of the
potential energy with respect to atomic positions, requires that the matrix of the second
derivatives of the potential energy
# 2E p # 2E p
!"
Fij = "
#ri! #rj
= % ! "
, (G6)
k, ! #r ik #r j!
k$ i, !$ j

called the force constants matrix, be positively definite4.

3 We, of course, assume that the moments of the forces also vanish.
4 This matrix determines the phonon spectrum and its positive definiteness also guarantees that the
corresponding eigenvalue problem for the vibrational frequencies has only real solutions. It follows
!"
from the requirement of translational invariance of the system that # Fi,j = 0 .
i,j
3

The quantities entering equations (G5) and (G6) must be taken as time averages in the
case of molecular dynamics, and ensemble averages in the case of Monte Carlo
simulations.

STRESS TENSOR IN THE SYSTEM OF PARTICLES

Equilibrium system at 0K
It is well known from the continuum mechanics that a medium can be in mechanical
equilibrium while it is subject to stresses. These stresses arise owing to application of
forces or displacements at the boundaries or arise locally as internal stresses due to
defects, thermal gradients and generally incompatibilities.
In a continuum the stress field (tensor), ! "# , is determined by equations of
equilibrium
3 !"
% !x#$ + F# = 0 (# = 1, 2, 3)
$=1 $

where F! is the α component of the body force (such as weight) per unit volume.
The physical meaning of these equations is that the total force is zero at any point of
the medium. These equations, together with the relevant boundary conditions and
constitutive laws relating stresses, strains and displacements (e. g. the Hook’s law),
determine fully the stress field ! "# . This field is generally varying locally within the
body and is a function of the position. The total stress per unit volume is
1
! "# = $ ! dV ,
total
V Volume "#
where V is the volume of the body and the integration extends over its whole volume
of the body. If no external loads are applied and no displacements (and/or strains) are
imposed at the boundary then in equilibrium ! "#total
is equal to zero.

The stress tensor, ! "# , which varies through the body, can be gauged by applying an
infinitesimally small strain defined by a strain tensor ! o"# . This strain tensor is not
related to the stress ! "# by the Hook’s law. The stress associated with the gauge
strain is infinitesimally small and negligible with respect to the internal stress
! "# . In this case the change of the potential energy of the body is, to the first order
in ! o"# ,
4

3
!E p = ' &" % dV ,
o
#$ #$
(G7)
#,$=1 V

where the integration again extends over the whole volume of the body.
Analogously as in the continuum, in a discrete structure the forces acting on
individual atoms vanish in equilibrium but there may be stresses due to applied loads
or sources of internal stresses. In order to measure the stress we again apply as a
gauge an infinitesimally small strain defined by a strain tensor ! o"# . Any vector rij
changes with the application of the strain ! o"# such that
3
r " r + % # !$ rij .
! !
o $
ij ij (G8)
$=1

In addition, the volume changes to the first order in ! o"# by

3 3
!V = V $ " = V $ " #% &#% ,
o o
## (G9)
# =1 #,%=1

The corresponding change of the potential energy of the discrete system is then
obtained by inserting (G8) into (G1). Expanding E p into the Taylor series with
respect to ! o"# we obtain to the first order in ! o"#
'3 "E p $ * o
!E p = & & & # rik , -#$ ,
) (G10)
#,$=1 ) i k "r ,
( k%i ik +
Comparing (G10) with (G7) and realizing that summation over all particles in the
discrete system is equivalent to integration over the volume of the continuous body,
the total stress per unit volume is in the discrete system
!E
! total
"#
= 1 $ $ "p rik# . (G11a)
V i k !rik
k"i

Using relation (G4c), which determines the force exerted on the particle i by the
particle k,

! total
"#
= $ 1 % % Fik" rik# . (G11b)
V i k
k!i
5

Equilibrium system at finite temperature

When the temperature of a system of particles is fixed, the total kinetic energy of the
particles must not change when applying the gauge strain tensor ! o"# . However, since
the velocity of the particle i is vi = dri dt , then using equation (G8) velocities of the
particles in the deformed state will change such that
3
v !i " v !i + % #!$
o
v$i (G12)
$=1

3
Expanding the kinetic energy E kin = 1 2 " " m i [v !i ]2 into the Taylor series with
!=1 i

respect to ! o
"#
gives to the first order in ! o
"#
3
% (
!E kin = $ ' $ m i v i v i * +"#
" # o
(G13).
",#=1 &
i )
However, if the temperature is fixed and thus the kinetic energy is to remain the
same, this term must be compensated by a term that arises due to a thermally induced
3
stress, ! T"# , which invokes the energy change !E = V & " #$
T o
% #$ that has the same
T

#,$=1

magnitude but opposite sign than !E kin . Hence

1
! T"# = $ % m i v"i v #i (G14)
V i
This is a generalization of the virial theorem. The total stress in the assembly of
interacting moving particles is then at any given time
( +
1 !E
! "#
total
= ' ** ' "p rik# % m iv"i v#i -- (G15a)
V i * k $rik -
) k&i ,

or using (G11b)
' *
1
! "#
total
= $ & )) & Fik" rik# + m iv"i v#i ,, (G15b)
V i ) k ,
( k%i +

The stress which would be measured is the time average of the stress given by
(G15a, b), ! "#
total
. In the case of molecular dynamics it is determined by time
6

averaging and in the case of Monte Carlo simulations as an ensemble average. (For
more details of evaluation of averages see sections on MD and MC methods).

If there is no directional flow and the movement of all the particles is on average
random, then in the three-dimensional case v!i v"i = 1 3 # !" v2i . The kinetic energy of
the randomly moving particles determines the temperature of the system according to
the equipartition theorem and in the three-dimensional case 1 2 ! m i v i = 3 2 Nk B T ,
2

i
where k B is the Boltzmann constant. The average thermally induced stress is then,
following equation (G14),
1 & "#
! "# = $ % m i v i v i = $ %
T " # 2
m i v i = $'k B T& "# (G16)
V i 3V i
where ! = N / V is the density of the material, measured as the number of particles per
unit volume. The average stress is in this case
1 $E p #
! "#
total
= && r ' (k BT)"# (G17a)
V i k $rik" ik
k%i
or
1
! "#
total
=$ & &
V i k
Fik" rik# $ 'k BT("# (G17b)
k%i
Obviously, the thermally induced stress does not contribute to the shear stresses but
only to the hydrostatic component of the stress tensor.

The hydrostatic pressure in the system is

1 3 1 3
p=! $ ## 3V #=1
3 #=1
" = $ $i $
k
Fik# rik# + &k BT , (G18)
k%i
3
since # ! "" = 3 .
"=1

In the case of non-interacting particles (ideal gas), when E p = 0 , we obtain

p = !k B T " pV = Nk B T = RT .
This is, of course, the well-known isotherm for the ideal gas. When the particles are
interacting the first two terms in equation (G18) contribute. The corresponding
isotherm of the gas of interacting particles is then
pV = RT + f(V),
7

where f(V) arises from the interaction term in equation (G18). This is the so-called
van der Waals isotherm.

When some external loads are applied, or boundaries of the system studied are held at
some fixed positions, the stress tensor ! "#total
is the stress induced by these loads
and/or constraints. However, if there are no loads or constraints, then in equilibrium
! "#
total
= 0, (G19)
For example, when considering the hydrostatic pressure, the requirement of p = 0
determines the equilibrium volume (density) and is equivalent to the condition
dH
= 0.
dV

However, the condition (G19) does not imply that there are no local internal stresses
since it only states that the average of all possible internal stresses is zero if external
loads or other constraints are not applied.

When determining the stress (at zero K) the potential energy was expanded to the first
order in !"#o
. Expansion of the potential energy to the second order in !"# o

determines the tensor of elastic moduli (see Appendix). The requirement that the
potential energy attains a minimum for zero strain leads to the condition that these are
positively definite. In fact, the condition that the force constants matrix (G6) is
positively definite already guarantees, together with the condition (G19), that the
elastic moduli are positively definite.

EXAMPLE: INTERACTIONS DESCRIBED BY A PAIR POTENTIAL

SUPPLEMENTED BY A VOLUME (DENSITY) DEPENDENT TERM

The potential energy of a system can be written as

1
2#
E p = U(V) + !(rij ) , (G20)
i, j
i" j

U(V) is the term dependent only on the total volume V or, in other words, only on
the average density, ρ, of the system. !(rij ) is a pair potential depending on the
separation, rij , of the atoms i and j and, possibly, the density ρ. The pre-factor 1/2
arises because the interaction between atoms i and j is counted twice, once when
evaluating the energy associated with the atom i and the second time when evaluating
the energy associated with the atom j.
8

When evaluating the forces on particles

!E p 1 % d#(r) rik" d#(r) rki" ( d#(rik ) rik"

= ' $ *= . (G21)
!rik" 2 '& dr r=r rik dr r=r rki *) drik rik
ik ki

Since rki! = "rik! the force exerted on the particle i by the particle k is

d#(rik ) rik!
Fik! =" . (G22)
drik rik
Following equations (G15a, b), the total stress tensor is
( #
+
! "#
total = 1 * d$(rik ) rik" rik -
' & m iv"i v#i - + dU ."# ;
& dr
V ** i,k rik
(G23a)
ik i - dV
) k%i ,

dU
the term ! arises due to the explicit dependence of the potential energy as given
dV "#
by (G20). Similarly as in (G17a)
" #
1 d$(rik ) rik rik dU
! total
"#
= & + ' ( )k B T' "# . (G23b)
V i,k drik rik dV "#
k%i

The total hydrostatic pressure is, following equations (G18) and (G16),

1 3
d"(rik ) (rik# )2 dU
p=! $ $
3V i,k #=1 drik rik
!
dV
+ &k BT (G24)
k%i

In the case of the cubic symmetry, when all quantities are invariant with respect to
the rotation by π/2 around the coordinate axes parallel to the cube axes, ! "# $ 0 for
! " # and

1 # d"(rik ) & dU 1
!11
total
= ! 22
total
= ! total
33 = * %
3V i,k %$ drik
rik ( +
(' dV
+
3V *
i
m iv2i (G25)
k)i

because " f(rik )(rik! ) 2 = 13 " f(rik )rik2 , where f(r) is a function dependent only on the
i, k i,k
magnitude of the vector r.
9

U(V) entering the potential energy is often set equal to zero, which means the energy
of the system is defined by the pair potential only (see for example the Lennard-Jones
potential). In other situation when this term is considered it is often approximated as
p0 (V ! V0 ) / V0 , where V is the current volume of the studied block of a given
material, V0 the equilibrium volume of the same block and p0 a constant pressure,
called the Cauchy pressure.
10

APPENDIX

ELASTIC MODULI
When applying a small homogeneous strain tensor, ! o"# , each vector rij changes as
described by equation (G8), assuming that no additional relaxations of atomic positions
occur owing to the application of the strain. This is the case when all the atoms in the
repeat cell are equivalent as, for example, in centro-symmetric structures but not in
general. However, we shall make this assumption at this stage. Furthermore, we shall
not consider the kinetics of the system and thus, effectively, 0K temperature is assumed.
In a continuum the change of the potential energy upon application of the strain tensor
o o
! "# can be written, to the second order in ! "# , as

) 3 3
o ,
!Ep = V + & " #$ % #$ + &
o o
1
2 C #$'( % #$ %'( . , (AG1)
* # ,$=1 # ,$,' ,( =1 -

where ! "# is the stress tensor and C !"#$ the tensor of second order elastic moduli. The
moduli satisfy the following symmetry relations:
C !"#$ = C "!#$ = C !"$# = C "!$#

The total volume changes such that to the second order in ! "#
) 3
1 3
1 3
,
!V = V +
*
& " #$
o
% #$ ' &
2 # ,$,( ,% =1
" #$
o
" o(% % #( % $% (1 ' % #$ ) + &
2 # ,$,( ,% =1
" #$
o
" o(% % #$ % (% (1 ' % #( ). (AG2)
-
# ,$=1

For the system composed of N interacting particles the change of the potential energy,
E p , to the second order in ! o"# , is obtained by inserting (G8) into (G1) and expanding
E p into the Taylor series with respect to ! o"# to the second order:

3 "E p 1 3 "2 E p
!E p = & & #
r $ o
ik #$
% + & & #
r$ r ) %o %o
( ik j! #$ ()
(AG3)
i,k #,$=1 "r ik
2 i, j,k,! #,$,( ,)=1 "r "r ik j!
k'i k'i,!' j
where the summation indices k and ! run over all atoms interacting with the atoms i and
j, respectively. Comparison of equations (AG1) and (AG3) yields for the total stress
tensor equation (G11a) and for the elastic moduli the following relation that satisfies the
above mentioned symmetry requirements
11

1 & % 2E % 2Ep ! $ % 2Ep " # % 2Ep ! # )

C!"#$ =
4V -
i, j,k,! (' % rik % rj!
" $
( ! # rik rj! + " # rik rj! + ! $ rik rj! + " $ rik rj! + (AG4)
p
% rik % rj! % rik % rj! % rik % rj! +*
k ,i,!, j

When additional relaxations of atomic positions occur, for example when the repeat cell
of the particle system contains non-equivalent atoms and there is no centro-symmetry,
the corresponding inhomogeneous atomic displacements are determined by the auxiliary
condition of zero forces on each atom of the strained medium. It was shown by Martin
(J. Phys. C: Solid State Phys., 8, 2837, 2858, 1975) that stresses are not affected by the
relaxation and are still given by equation (G11). However, the relaxation alters the
elastic moduli. They are now given by the relation
C!"#$ = C !"#$ + C! !"#$
*

in which C !"#$ is given by equation (AG4) and the relaxation part is

N N 3

!"#$ = % ( ( (D
!
C
i ij j
g &' D '#$
!"&
i=2 j= 2 &,' =1

1 $ E pot
2
where D i!"# = and g ij!" is the inverse of the force constants matrix
V $% !"$ri1#
1 # E pot
2

=
E ij!" when the origin of the repeat cell is identified with the atom number 15.
V #ri1! #r "j1
In practical calculations the evaluation of the elastic moduli is done by applying suitable
small strains to the block of atoms, relaxing, and evaluating the total energy as a
function of the applied strain. In such calculations the internal relaxations are
automatically included if the energy of the structure is minimized with respect to atom
positions after each application of the small strain. The elastic moduli are then obtained
by approximating the numerically calculated energy vs strain dependence by a second
or higher order polynomial and taking the appropriate second derivatives with respect to
the strain.

Bulk modulus
d 2 E pot
B =V , (AG5)
dV2
1 $V
Considering the strain tensor ! "# = % , which represents a pure dilatation, the
3 V "#
second, third and fourth terms in equation (AG3) give

5 The same type of the relaxation part of average elastic moduli arises in the continuum treatment of composite
materials when different components of the material possess different elastic moduli.
12

1 " !V % 1
2 3 ( 2Ep ) *
2 $# V '& 9 + + ) * rik rj!
i, j,k,! ) , * =1 ( rik ( rj!
k ,i,l , j

and therefore
1 3 ! 2Ep " #
B= $ $ " # rik rj! (AG6)
9V i, j,k,! " , # =1 ! rik ! rj!
k %i,!% j

Comparison with equation (AG4) gives then, as known from elasticity,

1 3
B = # C !!"" , (AG7)
9 ! ,"=1

Description of the potential energy in terms of pair potentials

The potential energy of the system is now given by equation (G20) and only terms of
! 2E p $ %
the type " # rik rik contribute in equation (AG4). For pair potentials these terms
!rik !r ik
are

! 2E p $ % 1 ( d 2 &(r ik ) 1 d&(rik ) + rik" rik$ rik# rik%

# rik r ik = * ' ,
"
!rik !r ik 2 ) drik2 rik drik -, rik2

Equation (AG4) then gives

1 -' d 2 %(rik ) 1 d%(rik ) * rik! rik" rik# rik$
C !"#$ = 1/
2V i,k /.)( drik2
&
rik drik ,+ rik2 (AG8)
i0 k

2
+
1 d%(rik )
4rik drik
( )
$!# rik" rik$ + $"# rik! rik$ + $!$ rik" rik# + $ "$ rik! rik# 4
43

+
dU 1
{ [$ $ (1 & $!# ) + $"! $ #$ (1 & $ "# ) + $!"$ $# (1 & $!$ ) + $"! $$# (1 & $"$ )]
dV 4 !" #$
d 2U
& 2 [$ !# $ "$ + $"# $!$ ](1 & $ !" )]} + V 2 $!" $ #$
1
dV
13

and using equation (G25) which defines the stress (without the kinetic term) we
obtain

1 -' d 2 %(rik ) 1 d%(rik ) * rik! rik" rik# rik$ 0

C !"#$ = 4/
2V i,k /.)( drik2
&
rik drik ,+ rik2
2
21
i3 k

+
1
($ 5 + $"# 5 !$ + $!$ 5 "# + $"$ 5 !#
4 !# "$
) (AG9)
+
dU 1
{[$ $ (4 & $!# & $"# & $ !$ & $"$ ) & $ !# $ "$ & $"# $!$
dV 4 !" #$
d 2U
& $ !$$ "# & $"$ $ !# ] & 2 [$ !# $ "$ + $"# $!$ ](1 & $ !" )]} + V 2 $ !"$ #$
1
dV

Cubic symmetry
There are three independent moduli:
c11 = C1111 , c12 = C1122 , c44 = C1212

1 # d 2 !(r ik ) 1 d!(rik ) & (r ik+ =1 )4 dU d 2U

c 11 = *%
2V i,k %$ drik2
" (
rik drik (' rik2
+ , 11 "
dV
+V 2
dV
k )i

1 # d 2 !(rik ) 1 d!(r ik ) & (rik+ = 1 ) 2 (rik+ = 2 )2 dU d 2U

c 12 = *%
2V i, j %$ drik2
"
rik drik ('
(
rik2
+
dV
+ V 2 (AG10)
dV
j) i

1 # d 2 !(rik ) 1 d!(r ik ) & (rik+ = 1 ) 2 (rik+ = 2 )2 1 dU

c 44 = * %
2V i, j %$ drik 2
"
rik drik ('
( 2
rik
+ , 11 "
2 dV
j) i

In equilibrium, when ! 11 = 0, we obtain

dU d 2U
c 12 ! c 44 =2 +V 2 (AG11)
dV dV
1 / 2(c 12 ! c 44 ) is called the Cauchy pressure and it is in equilibrium independent of
the pair potential. In the approximation in which U = p0 (V ! V0 ) / V0 the Cauchy
pressure is equal to p0 .
14

When the energy of a system of particles is determined solely by the pair potential, i.
e. if U = 0, then the Cauchy pressure is zero. This implies that if interaction in a
material is described only by a pair-potential then c 12 = c 44 , which is the so-called
Cauchy relation. This relation between elastic moduli is not satisfied for metallic and
covalent materials. However, it is almost true in a number of ionic solids, indicating
that in these materials the description of the total energy by pair-potentials is a
reasonable approximation.