Abstract
Although an old question, the electrostatic free energy of nonequilibrium solvation in a continuous dielectric has recently been disputed. Here we show that the nonequilibrium solvation energy can be obtained without any ambiguity by imposing a suitable external electric field with its source localized in the ambient so as to bring the nonequilibrium into an equilibrium state but constrain its charge distribution, polarization, and entropy unchanged. As an application, a two-sphere cavity model is proposed for estimating the solvent reorganization energy, which solves the longstanding issue that it tends to be overestimated by a factor of two by the popular continuum models.
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