Note on the physical basis of spatially resolved thermodynamic functions

TL;DR

This paper discusses the physical basis of spatially resolved thermodynamic functions, proposing a definition based on partial molar quantities and analyzing the consistency of existing theories with this definition.

Contribution

It introduces a rigorous physical definition of spatial resolution for thermodynamic functions and evaluates the consistency of existing computational methods with this definition.

Findings

First-order grid inhomogeneous solvation theory satisfies the new definition.

Grid cell theory most likely does not satisfy the definition.

The theory is consistent for an ideal gas in an external field at high temperature or weak fields.

Abstract

The spatial resolution of extensive thermodynamic functions is discussed. A physical definition of the spatial resolution based on a spatial analogy of partial molar quantities is advocated, which is shown to be consistent with how hydration energies are typically spatially resolved in the molecular simulation literature. It is then shown that, provided the solvent is not at a phase transition, the spatially resolved entropy function calculated by first-order grid inhomogeneous solvation theory (Nguyen et al. J. Chem. Phys., 137, 044101 [2012]) satisfies the definition rigorously, whereas that calculated by grid cell theory (Gerogiokas et al., J. Chem. Theory Comput., 10, 35 [2014]) most likely does not. Moreover, for an ideal gas in an external field, the former theory is shown consistent in the limit of weak field or high temperature whereas the latter is not. Finally, consistent with the proposed definition and with the case of an ideal gas in an external field, we derive an approximate expression for the solvent contribution to the free energy of solvation in the limit of infinite dilution from the spatial variation of the density around the solute.