Assessing the correctness of pressure correction to solvation theories in the study of electron transfer reactions

TL;DR

This paper evaluates pressure correction methods in liquid state theories for electron transfer reactions, finding that a theoretically grounded bridge correction is suitable while a posteriori corrections are inconsistent.

Contribution

It critically assesses two correction approaches for pressure overestimation in molecular density functional theory applied to electron transfer reactions.

Findings

A posteriori corrections violate the functional principle.

Bridge correction approach is theoretically sound and suitable.

A posteriori corrections lead to inconsistencies in free energy calculations.

Abstract

Liquid states theories have emerged as a numerically efficient alternative to costly molecular dynamics simulations of electron transfer reactions in solution. In a recent paper [Chem. Sci., 2019, 10, 2130], we introduced the framework to compute energy gap, free energy profile and reorganization free energy using molecular density functional theory. However, this technique, as other molecular liquid state theories, overestimates the bulk pressure of the fluids. Because of the too high pressure, the predicted free energy is dramatically exaggerated. Several attempts were made to fix this issue, either based on simple a posteriori correction or by improving the description of the liquid introducing bridge terms. By studying two model half reactions in water, Cl -> Cl+ and Cl -> Cl-, we assess the correctness of these two types of corrections to study electron transfer reactions. We found that a posteriori corrections, because they violate the functional principle, lead to an inconsistency in the definition of the reorganization free energy and should not be used to study electron transfer reactions. The bridge approach, because it is theoretically well grounded, is perfectly suitable for this type of systems.