Excess electrons in simple fluids. I. General equilibrium theory for classical hard sphere solvents

Abstract

In this paper we develop a theory for an excess electron in simple fluids. It is based upon the path integral formulation of quantum theory which maps the behavior of the electron on to that of a classical isomorphic polymer. The influence functional, i.e., the solvent induced potential between different sites on the polymer, is estimated from the RISM integral equation. The functional is not pair decomposable and the resulting polymer problem is not trivial to solve. The evaluation of the electron partition function and correlation functions is pursued with two approximations: (i) a mean field approximation which neglects the role of polymer fluctuations on the solvent induced interactions: (ii) a polaron approximation which is a linear approximation in the sense that it neglects large fluctuations in the polymer structure itself. The theory brings to light a new approach to the computation of multiparticle correlation functions in fluids, and the theory provides what appears to be a practical scheme for attacking a number of other problems including the analysis of polymer conformations in liquid environments. While this paper focuses on the role of packing forces in these systems, the theory can be generalized to include polarization and charge interactions as well.