High-Resolution Soft X-Ray Photoionization Studies of Selected Molecules

Near-edge soft x-ray photoionization spectra were measured for CO, SF{sub 6}, H{sub 2}S, and D{sub 2}S in the gas phase, using the Free University of Berlin plane-grating SX-700-II monochromator at the synchrotron radiation source BESSY. Photoionization spectra of carbon monoxide were measured near the carbon and oxygen K edges. Vibrational spacings and bond lengths are derived for several resonances. Results are consistent with equivalent-core model and indicate the different influences of the carbon and oxygen Is core holes. Corresponding spectra of H{sub 2}CO and D{sub 2}CO were also measured. Assignment of complex vibrational structure in valence-shell and Rydberg resonances is facilitated by comparison of spectra for the two isotopic species. Geometric and vibrational parameters are derived for several carbon 1s core-excited states. Isotopic shifts are observed in the energies and linewidths of some core-excited states. Sulfur hexafluoride photoionization spectra, measured near the sulfur L{sub 2,3} edges, show several series of weak, narrow Rydberg resonances. High resolution and good counting statistics allow a complete assignment of these states. Lineshapes of the broad inner-well resonances are analyzed to establish the magnitudes of vibrational and lifetime broadening in these states. Spectra of the H{sub 2}S and D{sub 2}S molecules were also measured nearmore » the sulfur L{sub 2,3} edges. Besides lower-energy transitions to inner-well states, a complex manifold of overlapping Rydberg resonances is observed. The rich fine structure of these states arises mainly from removal of orbital degeneracies in molecular field. Additional structure due to vibrational excitations in the final state is identified by comparison of the spectra for the two isotopic species.« less