Ab Initio Studies of Molecular Anions Stabilized in Point-Charge Lattices:Excited Electronic States of OH(-)

摘要

In an attempt to better understand the Ultraviolet absorption and emissionspectra of hydroxide ion, we have carried out what we believe are the first ab initio quantum chemical calculations on excited electronic states of this ion. Because these excited states all lie well above the ionization potential of hydroxide ion in vacuo, they are expected to be unstable with respect to autodetachment. This means that in the gas phase they can probably be detected only as resonances in electron scattering processes. This instability will also be evident in beyond-Hartree-Fock quantum calculations on such states, because with sufficient flexibility in the basis, the energy will tend toward that of a lower state of the neutral molecule. To render the excited electronic states computationally stable, we have surrounded the hydroxide ion by a simple point-charge lattice representative of the actual alkali halide lattices. Keywords: Ab initio theory, Diatomic anions, Impurity centers, Alkali, Halides, Reprints. (jg)