Lecture 12

Pair distribution functions

Background
Recall that the pair distribution function is ( )
( ( ) )

This quantifies the deviation of (r,r) from the non-interacting/independent result, which is ( ) ( ) ( )

If this system is system, i.e. no external fields, then the joint generic distribution is ( ) ( )

Isotropic, spherically symmetric system

For a general isotropic system, the joint generic distribution is ( ) ( )

If this system is spherically symmetric, then the pair distribution functions can be written as ( where | | ) ( )

g(r) has no center of mass dependence because it does not matter where you
are in the sample, i.e. where the center of mass is. This form of the pair distribution function only depends on the distances between particles.

Examples of g(r) for different pair potentials

Lets choose U as a sum of pair potentials ( ) (| |)

This choice is valid for a spherically symmetric particle/potential and the energy only depends on the distances between particles.

Choices for pair potential u(r)

A. Ideal gas For an ideal gas, u(r)=0 and therefore U(r1,,rN)=0. This means that there are no energy interactions between particles. Lets calculate g(r,r). ( )

This means that the radial distribution function g(r)=1 for r0. A consequence of this finding is the following: ( ) ( ) ( )

The second equality only holds true if the system is isotropic. B. Hard spheres The potential energy of interaction between two hard spheres is defined as follows: ( ) {

where is double the radius of the hard sphere. It turns out that the radial distribution function also depends on the statistical ensemble chosen to describe the system. For the canonical ensemble, ( ) ( | ) ( | ) ( | )

This means that the radial distribution function depends on the distance between particles, density, and temperature. Lets keep this in mind when we are considering g(r).

B-1. Dilute gas, <<3 or 3<<1

The plot of g(r) vs. r looks like a step function.

The distance between the hard spheres is in units of . Configurations where r< get pushed by repulsive forces and bunch up at r= to create the blip in the function.

B-2. Dense liquid, 31

Side note : tells you about the volume per particle : the volume that one particle excludes 31 tells us that the particles are taking up a lot volume, i.e. the allowed volume is almost completely filled by atoms. Its also interesting to note that hard spheres only have two phases, solid and liquid. Here is a schematic plot of g(r) vs. r.

The first bump at r= corresponds to the first solvation shell, which is depicted below for sodium ions being solvated by water.

The second bump corresponds to the second solvation shell, which falls just outside the first solvation shell. The hard sphere model is often used to model colloids and nanoparticles.