Calculating Entropies of Large Molecules in Aqueous Phase.

Abstract

Entropy benchmarking of different sized molecules in aqueous phase is carried out for known solvation models, where we compare geometry and solvation cavity packing parameters, which allows us to improve the accuracy of the obtained entropy values using empirical corrections. A comparison of solvation entropy models is conducted for a benchmarking set of 56 molecules, showing how an accurate description of cavitation entropy and its hindrance on other entropy values is important for large-sized solute molecules. Finally, we compare reaction free energies with entropies calculated using the most accurate solvation model considered, where we demonstrate a significant improvement in the accuracy relative to experimental values.