GROUND AND EXCITED-STATES OF CASH THROUGH ELECTRON PROPAGATOR CALCULATIONS

Electron propagator calculations of electron affinities of CaSH+ produce ground and excited state energies at the optimized, Cs minimum of the neutral ground state and at a C∞v geometry. Feynman-Dyson amplitudes (FDAs) describe the distribution of the least bound electron in various states. The neutral ground state differs from the cation by the occupation of a one-electron state dominated by Ca s functions. Described by FDAs with Ca-S π pseudosymmetry, corresponding excited states have unpaired electrons in orbitals displaying interference between Ca p and d functions. Above these lies a σ pseudosymmetry FDA with principal contributions from Ca d functions. Two FDAs with σ pseudosymmetry follow. Higher excited states exhibit considerable delocalization onto S. © 1990.