Solvation Model for Inner-Sphere Reorganization in the Photoionization of Univalent Anions in Solution

摘要

The energy of inner-sphere reorganization for the photoionization of univalent anions in aqueous solution is calculated from a discrete model of solvation. A multipole expansion is used to account for electrostatic interactions, and only the terms corresponding to nuclear motion are retained in the expansion to the exclusion of induced moments. London dispersion, Born repulsion, cavity formation and hydrogen bonding are also taken into account. The theory is applied to eight inorganic anions. Calculated reorganization energies are compared to experimental values deduced from threshold energies for photoelectron emission by aqueous solutions of eight anions in the 6 to 11 eV range of photon energies. Standard reduction potentials for the corresponding radical-anion couples are calculated from threshold energies and theoretical reorganization energies. Keywords: Vacuum Ultraviolet photoelectron spectroscopy.