Journal of Physical Chemistry, Vol.99, No.12, 4293-4305, 1995
Nonequilibrium Solvation - The Mutual Influence of Solute and Solvent Dynamics
A new approach for the study of the mutual influence of solute and solvent dynamics is presented. This method allows one to specify the solute-solvent Hamiltonian using the in vacuo solute potential and the nonequilibrium solvation free energy. A criterion to discard or to take into account the different solvent coordinates, depending on their influence on the solute dynamics, is established. Variational results are obtained using the global (two-dimensional) Hamiltonian and the two one-dimensional limits, SCF and BO. Two typical dynamic processes have been studied, the vibrational motion of a diatomic molecule and a proton transfer reaction in solution.
Keywords:ELECTRON-TRANSFER PROCESSES;TRANSITION-STATE THEORY;CHEMICAL-REACTIONS;CHARGE-TRANSFER;REACTION-PATH;PROTON-TRANSFER;POLAR-SOLVENTS;RATE-CONSTANT;MODEL;MOLECULES