INCLUSION OF NONEQUILIBRIUM CONTINUUM SOLVATION EFFECTS IN VARIATIONAL TRANSITION-STATE THEORY

We define a general set of effective solvent coordinates for reactions in solution that should be especially well suited for polar solvents. No specific functional form is assumed for the variation of charges with motions along or orthogonal to the reaction coordinate, and as a consequence the formalism allows the treatment of arbitrary reaction types using electronic structure calculations for the solute charge distribution. A critical assumption of the theory is that the nonequilibrium polarization field may be represented in terms of the adiabatic polarization fields that arise for linear geometric displacements. The results are combined with the Cartesian-coordinate canonical variational transition state theory presented previously to provide a general method for including both equilibrium and nonequilibrium solvation effects of a nondissipative, continuum-dielectric solvent in practical calculations of rate constants.