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.Comment: 8 pages, 6 figure