Middle 

East Technical University – Department of Metallurgical & Materials Engineering

Interatomic Potentials
Prepared and Presented by :

Assoc.Prof.Dr. Caner Şimşir

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 1/12

 The Cohesive Energy
 Cohesive energy (U) is the negative of the
energy needed to take all the atoms and
move them infinitely far apart :
N
U  E  all atoms    Ei
i 1

N
 1 N N   1 N N N  
U   v1  ri    `  ri , rj    `v3  ri , rj   .....
i 1 2 i 1 j 1 6 i 1 j 1 k 1

 v1 represents the effect of an external field (i.e. gravity, electric or magnetic field.).
 Φij is a sum over all pair of atoms or pair potential. Since it is an energy Φij= Φji.
 v3 is a three-body interaction

 Any interaction which involves more than two atoms is referred as many-body interaction.

 While pair potentials are adequate to describe many materials, there are important classes of
materials involving many-body terms, e.g., metals, covalent solids etc.

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 2/12

 Interatomic Potentials
 The simplest bonding occurs between rare-
gas solids. Interatomic potentials depend
entirely on the distance between the atoms.
 In an ionic material, the atoms are also
closed shell and the bonding is non-
directional. However, long range nature of
electrostatic forces should be considered.
 In metals, atoms are ionized with the
valence electrons distributed throughout the
system. The bonding has no directionality.
However, the interaction of delocalized
electrons should be reflected in interatomic
potentials.
 Covalent crystals have strong directional
bonds and directional nature of electronic
structure should be reflected in interatomic
potentials.
 Most systems are not strictly one type of
another. There may be some metals with
some covalency or partially ionic crystals.

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 3/12

 Basic Forms of Interatomic Interactions
 
ij  ri , rj   E  i  j   E  i   E  j 
Interactions at short Range:
 Repulsive force stems from
 Coulomb repulsion between ions
 Pauli exclusion principle
 The density of electrons decreases
exponentially with distance. So the short range
interaction can be modeled with:

SR  r   Be r
Non-bonding/ionic Interactions at long Range:
 Electrons are not static, they fluctuate around
their nucleus.
 When fluctuating, the dipole on one atom
interacts with the instantaneous dipole on the
other.
 For interacting, non-ionic, closed shell systems
this leads to an attractive term, referred as van
der Waals energy :
A
vdw  r    6
r
2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 4/12
 The Lennard‐Jones Potential
 The net potential has the form of:

B A
  r   12  6
r r
 It is usually rewritten into a dimensionally
more useful form:
   12   6 
  r   4       
 r   r  
 
 σ is the distance at which potential is zero
(ϕ(σ)=0)
 ε is the absolute value of the minimum of
the potential.
1
B 6 A2
   
 A 4B

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 5/12

 The Lennard‐Jones Potential
 The position of minimum potential (rm) is
rm  21/6 
 LJP can alternatively be expressed in terms
of rm as:

  rm 12  rm 6 
 r        
 r   r  
 
 It is also useful to express LJP in scaled (or
reduced) units in which energy is expressed
in terms of ε and distances in units of σ :

 1 1 
12 6

 r   4 *    *  
* *
 r   r  
 
 r
 r   r 
* *

 

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 6/12

 The Mie Potential (mn‐LJP)
 LJP can be improved by adding additional
adjustable parameters:
1
  mm  mn    m   n 
mn  r           
m  n  nn   r   r  
 The minimum point (rm) is given by:
1
m mn
rm    
n
 It can also be expressed in term of rm by:
10-6-LJP

n  rm 
m
m  rm  
n
LJP
mn  r         
m  n  r  n r  

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 7/12

 Born‐Mayer and Morse Potentials 
 Born-Mayer Potential can be expressed by:
C
  r   Ae  r
 6
r
 It can be rewritten in terms of rm as:

   rm  
6

 r    6e
  r  rm 
  rm   

 rm  6   r  

6 e m   rm7
r
A C
 rm  6  rm  6
 BMP is often used for ionic systems.
10-6-LJP
 Arising from the simple theory of bond potentials,
the Morse Potential takes the form of : LJP

 
BMP
  r    e2  r  r   e  r r
m m 
MP
 Morse potential is sometimes used in modeling
interatomic interactions in metals.

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 8/12

 Analytical Lattice Sums
 Interatomic potential that are functions only
the distance between atoms is referred as
central-force potentials.

   12   

6

u  r   2  A12    A6   
 r  r  
 
1/6
 2 A12 
r0      1.09
 A6 
1/2
 2 A12 
v0     3
 0.916 3

A
 6 
3
A 
2
u0      8.6
6

2  A12 
u0 
B0  8  75 3
v0 
2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 9/12
 Evaluating LJ Model for Solids
 Using potential parameters and analytical sums, 0K
cohesive properties of rare-gas solids can be
calculated.
 All these materials form FCC solids in equilibrium as
do all systems described by LJP.
 Regarding the calculated r0 values, the largest
deviation is in Ne, which, being a very light atom, has
a large zero-point motion, which tends to lead to
larger lattices.
 u0 and v0 represents a single point in the curve. On
the other hand B0 is a function of the shape of the
curve at the equilibrium point.
 LJP does much less well for systems under
pressure, in which nearest-neighbors are forced up
the repulsive wall.

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 10/12

 Central Force Potentials and the Properties of Solids
 Interatomic potential that are functions only
the distance between atoms is referred as
central-force potentials.
 Perfect crystal with a single component
whose interactions are describe by central-
force potentials will always take on simple
structures like FCC, BCC etc.
 Thus CFP cannot be used to model pure
systems with complicated structures.
 There is also experimental evidence that
using central-force potential cannot provide
adequate description of elastic behavior of
solids.
 Deviation from Cauchy relation (c12\c44=1)
can be used as a measure of applicability of C12\C44>1 for metals
CFPs in modeling of certain materials.
C12\C44<1 for covalent bond

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 11/12

 Middle East Technical University – Department of Metallurgical & Materials Engineering

Thanks for listening.
Prepared and Presented by :

Assoc.Prof.Dr. Caner Şimşir

2019 Spring METE 350 – Multi‐scale Modeling & Simulation in Materials Sci.&Eng. 12/12