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Published October 15, 1992 | Published
Journal Article Open

Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of SiF

Abstract

Results of calculations of rotationally resolved photoelectron spectra for resonance enhanced multiphoton ionization (REMPI) of SiF via the B ^2Σ^+ (4sσ), C" ^2Σ^+ (4pσ), and C' ^2Π (4pπ) Rydberg states are reported. In addition to the expected ΔN=even peaks, unusually strong ΔN=±1 transitions are predicted for photoionization of the B ^2Σ^+ state. These unusual transitions are due to even angular momentum components of the photoelectron matrix element and arise from the formation of Cooper minima in the ionization channels and strong l mixing in the electronic continuum induced by the nonspherical molecular ion potential. Unexpected ΔN=0,±2 transitions, due to odd wave contributions to the photoelectron matrix element, are also predicted for photoionization of the C" ^2Σ^+ state. Asymmetrical ion distributions with respect to ΔN=0 are also predicted for the C' ^2Π state. Cooper minima are predicted to occur in the l=2 wave of the kπ photoelectron channel for the B state and in the l=4 wave of the kσ and kπ channels for the C' state. Photoelectron angular distributions provide further insight into the photoionization dynamics.

Additional Information

© 1992 American Institute of Physics. (Received 9 June 1992; accepted 6 July 1992) This work was supported by grants from the National Science Foundation, 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 CRA Y Y-MP2E/116 Supercomputer.

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August 20, 2023
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