Rotationally resolved photoionization of polyatomic hydrides: CH_3, H_2O, H_2S, H_2CO

Abstract

Combined theoretical and experimental studies of rotationally resolved photoelectron spectra for single‐photon ionization of the outermost valence orbitals of H_2O, H_2S, H_2CO, and CH_3 are reported. Agreement between calculated and measured spectra is very encouraging. Both show that photoionization dynamics is very molecular in origin for H_2O, H_2S, and H_2CO but quite atomiclike for CH_3. Parity selection rules and the angular momentum composition of the photoelectron are used to illustrate the dynamical aspects of photoionization of polyatomics as molecular symmetry changes in a group of structurally related systems.

Additional Information

© 1994 American Institute of Physics. (Received 19 November 1993; accepted 23 December 1993) Work at the California Institute of Technology was supported by grants from the Air Force Office of Scientific Research and the Office of Health and Environmental Research of the U.S. Department of Energy. We also acknowledge use of resources of the Jet Propulsion Laboratory/Caltech CRAY Y-MP2E/232 Supercomputer. Work at Brookhaven National Laboratory was supported under Contract No. DE-AC02-76CH00016 with the U.S. Department of Energy and by its Division of Chemical Sciences, Office of Basic Energy Sciences.

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