Abinitioconfiguration interaction study of the Rydberg states of O2. I. A general computational procedure for diabatic molecular Rydberg states and test calculations on the3Pgr;gstates of O2

摘要

Configuration interaction calculations have been performed on the3Pgr;gsymmetry of O2which establish a general computational procedure for diabatic molecular Rydberg states. Three different calculations which include varying amounts of electronic correlation for the Rydberg and valence states are reported. The interaction potentials for the lowest diabatic Rydberg state from these three calculations are in excellent agreement showing that semihyphen;internal correlation energy of Rydberg states has little effect on the potential curves. The Rydberg state is found to be exceedingly similar to the O2+2Pgr;gstate to which the3Pgr;gRydberg series converges. Energies for the lowest four Rydberg vibrational levels are presented.