Thermodynamics of Hydration from the Perspective of the Molecular Quasi-Chemical Theory of Solutions

TL;DR

This paper discusses the molecular quasi-chemical theory (QCT) as a framework for understanding and calculating hydration phenomena, emphasizing its versatility in handling diverse solutes and interactions.

Contribution

It introduces and elaborates on the molecular quasi-chemical theory (QCT) for hydration, highlighting its conceptual and practical advantages across various solutes.

Findings

QCT regularizes complex thermodynamic problems.

It effectively models diverse solutes from ions to macromolecules.

Guides on approximations improve calculation efficiency.

Abstract

The quasi-chemical organization of the potential distribution theorem -- molecular quasi-chemical theory (QCT) -- enables practical calculations and also provides a conceptual framework for molecular hydration phenomena. QCT can be viewed from multiple perspectives: (a) As a way to regularize an ill-conditioned statistical thermodynamic problem; (b) As an introduction of and emphasis on the neighborship characteristics of a solute of interest; (c) Or as a way to include accurate electronic structure descriptions of near-neighbor interactions in defensible statistical thermodynamics by clearly defining neighborship clusters. The theory has been applied to solutes of a wide range of chemical complexity, ranging from ions that interact with water with both long-ranged and chemically intricate short-ranged interactions, to solutes that interact with water solely through traditional van~der~Waals interations, and including water itself. The solutes range in variety from monoatomic ions to chemically heterogeneous macromolecules. A notable feature of QCT is that in applying the theory to this range of solutes, the theory itself provides guidance on the necessary approximations and simplifications that can facilitate the calculations. In this Perspective, we develop these ideas and document them with examples that reveal the insights that can be extracted using the QCT formulation.