An integral equation theory for solvation effects on the molecular structural fluctuation.

Abstract

A new integral equation theory is proposed, which enables us to efficiently compute conformational distribution of a polyatomic molecule in solution phase. The solvation effect on the intramolecular correlation function is evaluated through a self-consistent procedure. In addition, the analytical expression of solvation free energy is derived, explicitly taking into account the molecular structural fluctuation. The derived equation establishes a direct route between the structural fluctuation and free energy of the molecule. The method was successfully applied to a series of n-alkanes in aqueous solutions to demonstrate the superiority of the proposed theory.