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Theory of band shape formation in Auger and autoionization decay in molecules is presented and numerically applied to spectra of the CO molecule. In particular, the role of lifetime vibrational interference in the various vibronic decay channels is elucidated. New high resolution Auger and autoionization spectra are presented. The calculated band shapes are compared with the experimental recordings. The vibronic spectra of the intermediate states in the Auger and autoionization decay are analyzed and compared with available ESCA and EELS spectra, respectively. The role of the electron correlation on the formation of the core state potential surfaces is investigated in that connection. The assignment problem of the outer part of the CO Auger spectrum is reinvestigated and the effect of interference due to hole mixing in the wave functions is pointed out. The time dependent Franck–Condon (FC) formalism used to derive the lifetime vibrational interference is shown to have a bearing on the analogy of the sudden approximation for electron ionization with the FC principle for vibronic excitations and makes possible a derivation of the lifetime for the vertical vibrational state in electron ionization.

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