A continuum reaction field theory of polarizable, nondipolar, quadrupolar solvents: Ab initio study of equilibrium solvation in benzene

Abstract

A continuum theory to describe solvation in nondipolar quadrupolar solvents is developed by accounting for electronic polarizability. A general Hamiltonian for a solute–solvent system in an arbitrary nonequilibrium configuration is obtained in terms of two field variables—densities of the solvent quadrupole and induced dipole moments. Equilibrium solvation is studied by optimizing this Hamiltonian with account of cavity boundaries. As an application, electronic structures and free energies of small molecules in benzene are examined with ab initio methods. Solvation stabilization due to solvent quadrupole moments is found to be substantial; for the solutes considered here, it is comparable to and often in excess of that arising from solvent-induced dipole moments.