Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. II. Molecular-frame and...

Experimental and theoretical results for molecular-frame photoemission are presented for inner-valence shell photoionization of the CO molecule induced by linearly and circularly polarized light. The experimental recoil frame photoelectron angular distributions (RFPADs) obtained from dissociative photoionization measurements where the velocities of the ionic fragment and photoelectron were detected in coincidence, are compared to RFPADs computed using the multichannel Schwinger configuration interaction method. The formalism for including a finite lifetime of the predissociative ion state is presented for the case of general elliptically polarized light, to obtain the RFPAD rather than the molecular frame photoelectron angular distribution (MFPAD), which would be obtained with the assumption of instantaneous dissociation. We have considered photoionization of CO for the photon energies of 26.0 eV, 29.5 eV, and 32.5 eV. A comparison of experimental and theoretical RFPADs allows us to identify the ionic states detected in the experimental studies. In addition to previously identified states, we found evidence for the 2 (2)Δ state with an ionization potential of 25.3 eV and (2)Σ(+) states with ionization potentials near 32.5 eV. A comparison of the experimental and theoretical RFPADs permits us to estimate predissociative lifetimes of 0.25-1 ps for some of the ion states. Consideration of the MFPADs of a series of (2)Π ion states indicates the importance of inter-channel coupling at low photoelectron kinetic energy and the limitations of a single-channel analysis based on the corresponding Dyson orbitals.