Statistical Molecular

Thermodynamics
Christopher J. Cramer
Video 2.7
Other Intermolecular Potentials

Molecular Interaction
The virial expansion derives from exact relationships
between virial coefficients and intermolecular interactions
r

If 2 molecules interaction according to a potential energy

function that depends only on their separation r, then B2V
can be expressed as:

u(r) kB T 2
B2V (T) = 2N A 0 e
1r dr

Understanding Attraction
We can understand the r6 attraction term in the L-J potential
dipole-induced dipole interactions
dipole-dipole interactions

ud ,d (r) =

+
2

12 2
221
uinduced (r) =

2
2
( 40 ) r 6 (4 0 ) r 6

averaged over
all orientations

dispersion interactions

induced dipole-induced dipole interactions

212 22

1
2
6
r
4
3k
T
( 0) ( B )

All terms have same r6 behavior, but

for nonpolar molecules only the

dispersion interactions are relevant

udisp (r) =

3
I1I2 1 2
1
2 ( I1 + I2 )( 4 0 ) 2 r 6

Quantum Mechanical Dispersion

This is a quantum mechanical effect associated with
the correlated motion of the electrons in the atoms,
which leads to a reduction in energy.
+

ionization energy (J)

polarizability (Cm2V-1)

3
I1I2 1 2
1
udisp (r) =
2 ( I1 + I2 )( 4 0 ) 2 r 6
permittivity of vacuum (C2J-1m)

Fritz London

Dispersion is generally the

dominant contribution to the
r6 term

Other Intermolecular Potentials

Simpler u(r) models lead to analytical solutions for the
integral that defines B2V(T)

hard-sphere

square-well

potential

potential

u(r < ) =
u( < r < ) =
u(r > ) = 0

u(r < ) =
u(r > ) = 0

The Hard Sphere Model

u(r < ) =
u(r > ) = 0

Good for very high T relative to /kB

u(r) kB T 2
B2V (T) = 2N A 0 e
1r dr

= 2N A [0 1]r dr 2N A [e 1]r dr
0

2 3 N A
=
This is 4 times the volume of NA
3
spheres ( in this case can be thought
of as the sphere diameter)

Independent of T, but B2V(T) vs T plot is reasonably flat at high T

The Square Well Model

same as hard sphere

kB T
2 3 N A
3
B2V (T) =
1
1 ( 1)e

u(r < ) =
u( < r < ) =
u(r > ) = 0

Good fit to experimental

data for N2

sqwm

L-J

328

370

/kB (K) 95.2

95.1

(pm)

1.58