MOLECULAR RESPONSE METHOD FOR SOLVATED MOLECULES IN NONEQUILIBRIUM SOLVATION

We present an extension of the molecular response method of solvated c ompounds, The extension treats in a proper fashion the effects of none quilibrium solvation on the molecular properties of the solvated compo und. The molecular properties evaluated within the response formalism are properties that are measured using high-frequency electromagnetic fields. We consider the changes in the molecular properties due to non equilibrium solvation. The nonequilibrium solvation arises from change s in the molecular charge distribution induced by the high-frequency p erturbation. The optical polarization vector is al all times assumed t o be in equilibrium with the charge distribution of the solute, contra ry ro the inertial polarization, which is not necessarily in equilibri um with the charge distribution of the solute. We calculate shifts of excitation energies and frequency-dependent polarizabilities as a func tion of the optical and static dielectric constants.