Dynamic effects of nonequilibrium solvation;Potential and free energy surfaces for Z/E isomerization in solvent-solute coordinates

摘要

A novel definition of a solvent coordinate associated with a given reaction is formulated in terms of molecular-dynamic trajectories of the solvent and is applied to discuss the topography of potential energy and free energy surfaces of model liquid phase Z/E isomerization reactions in solvent-solute coordinates.It is shown that the arrangement of the reactant and product valleys on these surfaces can vary from consecutive to parallel,depending on the strength of the solvent-solute interactions.