Computed electronic energy levels of HF+ and the interpretation of photoelectron spectroscopic data

Abstract

Ab initio matrix Hartree-Fock wave functions are calculated for the X²Π_i and A²Σ⁺ states of HF⁺ at a series of internuclear distances. From the computed potential curves and consideration of the differences in correlation energy between the two levels, estimates of the excitation energy and spectroscopic properties of these levels are made. These enable an interpretation of the photoelectron spectrum of HF to be given. The results are in close agreement with one of the two empirical interpretations of the spectrum.