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.
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A possibility cannot be excluded that the procedure is failed—for example, Δω has multiple numerical solutions—when it is applied to a more complicated system such as polymer. Further modification of the theory may be necessary to treat such a system; for example, solvent effects on the scaling laws and Flory exponents governing the radius of gyration are analysed.
