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Inner-valence states of CO+ between 22 eV and 46 eV studied by high resolution photoelectron spectroscopy and ab initio CI calculations

Photoionization of the CO molecule and inner-valence states of CO+ between 22 and 45 eV have been studied by means of photoelectron spectroscopy using both synchrotron radiation and He II radiation. Vibrational structure has been resolved in many bands up to 45 eV. CASSCF (complete active space self-consistent field) and MRCI (multireference configuration interaction) calculations of potential curves in the 22-30 eV range have been performed and these have been used to predict vibrational levels and Franck-Condon factors. In this energy range three valence states, D 2II, 32 Sigma + and 32II have been identified, and spectroscopic constants have been determined for the first two of these. Above 30 eV, all valence states have been found to be repulsive. In addition to the broad bands expected for these states, several progressions of narrow lines are observed most probably reflecting transitions to Rydberg states.