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Penning ionization electron spectroscopy of the CO molecule by He* (21S) metastable atoms is studied. Vibrational populations are reported for the three energetically accessible states of the CO+ ion (X2Σ+, A2 Π and B2Σ+). An obvious discrepancy is observed between the excited vibrational levels of the X2Σ+ state and the calculated Franck-Condon factors. This result is attributed to an excitation transfer process via Rydberg vibrational progression converging to the CO+ (D2 Π) ionic state in agreement with the recent observations by fluorescence of neutral dissociate states. The presence of electrons coming from the well-known σ shape resonance is not excluded

Excitation Transfer Process in Penning Ionization of the CO Molecule by Helium Atoms in Singlet Metastable State