Vibrational structure in core-level photoelectron spectra: Periodic trends

Z. F. Liu, G. M. Bancroft, J. N. Cutler, D. G. Sutherland, K. H. Tan, J. S. Tse, and R. G. Cavell
Phys. Rev. A 46, 1688 – Published 1 August 1992
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Abstract

High-resolution (∼0.1 eV) core-level photoelectron spectra of gas-phase SiH4, PH3, GeH4, and AsH3 have been recorded using monochromatized synchrotron radiation. These spectra, multiconfiguration self-consistent-field calculations of the vibrational profile, and the core-equivalent model all show that core-level vibrational structure decreases dramatically, both down a group of congeneric molecules and across a periodic row of isoelectronic molecules. The theoretical calculations also show that the Franck-Condon factors do not change for relatively shallow core levels (e.g., Si 2p,2s or Ge 3d,3p) but increase significantly for deep core levels (e.g., Si 1s).

  • Received 21 February 1992

DOI:https://doi.org/10.1103/PhysRevA.46.1688

©1992 American Physical Society

Authors & Affiliations

Z. F. Liu, G. M. Bancroft, J. N. Cutler, D. G. Sutherland, and K. H. Tan

  • Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A 5B7
  • Canadian Institute for Synchrotron Radiation, The University of Western Ontario, London, Ontario, Canada N6A 5B7
  • Canadian Synchrotron Radiation Facility, Synchrotron Radiation Center, University of Wisconsin, Stoughton, Wisconsin 53589

J. S. Tse

  • Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6

R. G. Cavell

  • Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2

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Vol. 46, Iss. 3 — August 1992

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