POLARIZATION-CORRELATED SOLUTE-SOLVENT STATES

We introduce a new formulation of the joint electronic states of a solute and a solvent for the situation in which the solute has weakly coupled, low-lying states whose mixing must be determined. A typical solute might be an electron-donor-acceptor complex (DA) whose ionic state (D+ A-) is coupled to a neutral, locally excited state, (D* A) or (DA*), of similar energy. The key feature of the treatment is that the electronic state and polarization of the solvent are allowed to correlate with those of the solute. With the present formulation, unlike earlier formulations, degeneracies are treated realistically, and different eigenstates are orthogonal. The problem of evaluating the orientational polarization of the solvent is left to future work.