Rotationally Resolved Photoionization With Coherent Vuv Radiation

Pulsed field ionization (PFI) has been used in conjunction with coherent VUV radiation to investigate the rotational state distributions of molecular cations following single photon ionization. The rotational state distributions for several linear cations (O2, NO, OH(OD), HCl and N20 can be interpreted predominately on the basis of the near-threshold, one-electron photoionization dynamics; however, field-induced autoionization is often the dominate ionization pathway for rotational branches involving negative changes in core angular momentum. For photoionization of the H2X (X = 0, S) non-linear triatomic molecules, transitions between asymmetric top levels involving the rotational angular momentum projections, K{sub a} and K{sub c} permit resolution of the photoelectron continua according to symmetry. The observed spectra clearly demonstrate the importance of the non-spherical nature of the molecular ion potential which leads to photoelectron final states which are unexpected from atomic-like analogies.