Balancing Local Order and Long-Ranged Interactions in the Molecular Theory of Liquid Water

TL;DR

This paper develops a molecular theory of liquid water based on computer simulations, balancing local order and long-range interactions, and demonstrates its effectiveness in predicting thermodynamic properties.

Contribution

It introduces a novel theoretical framework that combines quasi-chemical theory with a regularized approach to long-range interactions for liquid water.

Findings

Gaussian approximation accurately predicts Gibbs free energy

Unimodal binding-energy distributions observed in simulations

Subtle thermodynamic discrepancies highlight complex water behavior

Abstract

A molecular theory of liquid water is identified and studied on the basis of computer simulation of the TIP3P model of liquid water. This theory would be exact for models of liquid water in which the intermolecular interactions vanish outside a finite spatial range, and therefore provides a precise analysis tool for investigating the effects of longer-ranged intermolecular interactions. We show how local order can be introduced through quasi-chemical theory. Long-ranged interactions are characterized generally by a conditional distribution of binding energies, and this formulation is interpreted as a regularization of the primitive statistical thermodynamic problem. These binding-energy distributions for liquid water are observed to be unimodal. The gaussian approximation proposed is remarkably successful in predicting the Gibbs free energy and the molar entropy of liquid water, as judged by comparison with numerically exact results. The remaining discrepancies are subtle quantitative problems that do have significant consequences for the thermodynamic properties that distinguish water from many other liquids. The basic subtlety of liquid water is found then in the competition of several effects which must be quantitatively balanced for realistic results.