Density functional theory of nonuniform polyatomic systems. II. Rational closures for integral equations

Abstract

With the density functional theory outlined in paper I, we address and formally solve the nonlinear inversion problem associated with identifying the entropy density functional for systems with bonding constraints. With this development, we derive a nonlinear integral equation for the average site density fields of a polyatomic system. When external potential fields are set to zero, the integral equation represents a mean field theory for symmetry breaking and thus phase transformations of polyatomic systems. In the united atom limit where the intramolecular interaction sites become coincident, the mean field theory becomes identical to that developed for simple atomic systems by Ramakrishnan, Yussouff, and others. When the external potential fields are particle producing fields (in the sense introduced long ago by Percus), the integral equation represents a theory for the solvation of a simple spherical solute by a polyatomic solvent. In the united atom limit for the solvent, the theory reduces to the hypernetted chain (HNC) integral equation. This reduction is not found with the so-called ‘‘extended’’ RISM equation; indeed, the extended RISM equation—the theory in which the HNC closure of simple systems is inserted directly into the Chandler–Andersen (i.e., RISM or SSOZ) equation—behaves poorly in the united atom limit. The integral equation derived herein with the density functional approach however suggests a rational closure of the RISM equation which does pass over to the HNC theory in the united atom limit. The new integral equation for pair correlation functions arising from this suggested closure is presented and discussed.