Introducing temperature dependence in an enhanced Poisson–Boltzmann approach

Continuum solvation models have traditionally been developed for room temperature only, yet many simulation methods incorporating continuum solvation treat temperature as an adjustable system parameter. In this communication we study the suitability of a generalized continuum solvation model to be converted into a temperature-dependent variant. A prototype is developed and its general performance analyzed. The approach followed here is solely based on fundamental physical relations and allows for a detailed analysis of relative importance of different partial contributions. A dominant role for cavitation is discovered but little difference is seen between different types of chemical compounds. This has important consequences on entropy trends in general.