Reaction Entropies in Solution from Analytical Three-Dimensional Reference Interaction Site Model Derivatives with Application to Redox and Spin-Crossover Processes

An analytical approach to compute the excess entropy of solvation at constant pressure in three-dimensional reference interaction site model (3D-RISM) calculations is presented. It includes the changes in the macroscopic dielectric constant of the solvent upon variation of temperature and density. The approach is exact within the framework of force-field descriptions of the solute and gives reasonable results for self-consistently determined electrostatics as used in the 3D-RISM-self-consistent field approach, particularly for entropy differences. The new method is applied to simple examples of reaction entropies of iron complexes in aqueous solution, for which simple gas-phase calculations and many other approaches give unreliable estimates. For both redox half-reactions and spin-crossover processes, (semi)quantitative agreement with experimental reaction entropies can be achieved out of the box.

Automated summary

This article presents an analytical approach to compute the excess entropy of solvation at constant pressure in 3D-RISM calculations. The approach considers changes in the macroscopic dielectric constant of the solvent with temperature and density variations. It gives reasonable results for self-consistently determined electrostatics, particularly for entropy differences, and shows promise in obtaining (semi)quantitative agreement with experimental reaction entropies.