Solvent Mean Force Perturbations of Molecular Vibration, Isomerization and Dissociation

摘要: The mean force potential represents the effect of solvent-solute interactions on solvation thermodynamics, and thus solute chemical potentials equilibrium constants. Chemical reaction dynamics, other hand, may involve additional non-equilibrium contributions to short-lived intermediates. Nevertheless, solvent places significant constraints dynamics as well thermodynamics by defining structure entire reactive surface. Perturbed hard sphere fluid theories [1, 2, 3], which make optimal use analytical Statistical mechanical expressions for thermodynamic properties fluids in predicting real liquids, offer an appealing formalism modeling such effects [4, 5, 6].