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Liquid states theories have emerged as a numerically efficient alternative tocostly molecular dynamics simulations of electron transfer reactions insolution. In a recent paper [Chem. Sci., 2019, 10, 2130], we introduced theframework to compute energy gap, free energy profile and reorganization freeenergy using molecular density functional theory. However, this technique, asother molecular liquid state theories, overestimates the bulk pressure of thefluids. Because of the too high pressure, the predicted free energy isdramatically exaggerated. Several attempts were made to fix this issue, eitherbased on simple a posteriori correction or by improving the description of theliquid introducing bridge terms. By studying two model half reactions in water,Cl -> Cl+ and Cl -> Cl-, we assess the correctness of these two types ofcorrections to study electron transfer reactions. We found that a posterioricorrections, because they violate the functional principle, lead to aninconsistency in the definition of the reorganization free energy and shouldnot be used to study electron transfer reactions. The bridge approach, becauseit is theoretically well grounded, is perfectly suitable for this type ofsystems.

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