Perturbation theory for water with an associating reference fluid.

Abstract

The theoretical description of the thermodynamics of water is challenged by the structural transition towards tetrahedral symmetry at ambient conditions. As perturbation theories typically assume a spherically symmetric reference fluid, they are incapable of accurately describing the liquid properties of water at ambient conditions. In this paper we address this problem by introducing the concept of an associated reference perturbation theory (APT). In APT we treat the reference fluid as an associating hard sphere fluid which transitions to tetrahedral symmetry in the fully hydrogen bonded limit. We calculate this transition in a theoretically self-consistent manner without appealing to molecular simulations. This associated reference provides the reference fluid for a second order Barker-Henderson perturbative treatment of the long-range attractions. We demonstrate that this approach gives a significantly improved description of water as compared to standard perturbation theories.