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

Abstract

Liquid state theories have emerged as a numerically efficient alternative to costly molecular dynamics simulations of electron transfer reactions in solution. In a recent paper [Jeanmairet et al., Chem. Sci. 10, 2130-2143 (2019)], we introduced the framework to compute the 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 fluid. Because of the very 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 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 correction, because it violates the Variational principle, leads 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.