The number of configurations in an assembly and cooperative phenomena

Abstract

We consider an ideal problem of adsorption of single and double particles upon a solid surface which has its sites of accommodation regularly arranged, and by comparing the equilibrium properties obtained by Bethe's method with the ordinary statistical formulae, we obtain approximate expressions for:(1) g(N, n, X), the number of ways of arranging n particles upon N sites of a lattice so that the number of neighbouring sites occupied by the particles is X.(2) g2(N, n, X), the number of ways of arranging n double particles upon N sites so that each of the double particles takes up two adjacent sites and the number of neighbouring sites occupied by two different particles is X.Both these expressions are found to agree with the exact values when the N sites lie on a straight line. When we use the first expression to construct the configurational partition functions of certain physical assemblies and expand them in powers of 1/kT, they are found to agree with the corresponding rigorous expressions as far as (1/kT)3, which is the highest power which we can find rigorously at present. With the help of the first expression, formal equations for superlattice formation in an alloy with the composition 1: 1 and equations for the separation into phases of regular liquids are given. Lastly we show that atoms and molecules in a regular liquid may dissociate or recombine suddenly accompanied by a latent heat. This is a new cooperative phenomenon, which may bear some resemblance to the melting process between the solid and liquid states.