Quasi-Chemical Equilibrium Theory, Part II

Abstract

The quasi-chemical equilibrium, or pair correlation, approximation to statistical mechanics is written in terms of second-quantization formalism. This involves an entension of the original theory to include an Ansatz for off-diagonal elements of the density matrix. The formal expressions involve “labelling operators” acting in a purely formal Hilbert space. These labelling operators obey Bose commutation rules for correlations between even numbers particles (e.g. pair correlations), Fermi commutation rules for correlations between odd numbers of particles. The labelling operators provide an algebraic way of formulating the restriction to certain types of “graphs”. We also show how to include higher-order correlations into the Ansatz. The main results of the original theory can be derived more rapidly with the new formalism. However, certain correction terms obtained earlier are shown to be in error, necessitating a reinvestigation of the nature of the condensation phenomenon. This re-investigation is carried out in two following papers, and proves to lead to no essential modifications of the previous results. The correlation matrices which enter into the Ansatz need to be related to the Hamiltonian of the system, and to the thermodynamic variables which define its thermodynamic state. A variational formulation is developed for this purpose, but no explicit calculations are carried out in this paper.