Triplet correlations and bridge functions in classical density functional theory for liquid water

Abstract

Density functional theory for molecular fluids developed by Donley et al. (J. Chem. Phys. 101 (1994) 3205) is extended to include the effects of orientation-dependent bridge functions associated with the inter-particle, triplet correlations. Resultant integral equations for the pair and direct correlation functions are solved for water, where the three-body direct correlation functions are approximated in terms of two-body functions. A test calculation employing a simple Gaussian form for the two-body function between the oxygen sites then provides a promising result to improve the description of the oxygen–oxygen correlations in liquid water at room temperature.