Heterogeneous solvation: An ab initio approach

A multiconfigurational self-consistent reaction field (MCSCRF) method is pr esented for solvation of a molecule on a metal surface. We assume that the molecular system is enclosed in a half-spherical cavity and adsorbed on the surface of a perfect conductor. The half-spherical cavity is embedded in a linear, homogeneous, isotropic dielectric medium. A multiconfigurational s elf-consistent reaction field linear response method is presented for calcu lating frequency dependent polarizabilities as well as electronic excitatio n energies and transition moments of a solvated molecule on a metal surface . (C) 2001 American Institute of Physics.