APS » PROLA » Phys. Rev. A » Volume 67 » Issue 2
< Previous article | Next article >

Phys. Rev. A 67, 022714 (2003) [7 pages]

Influence of chemical bonds on the lifetime of the molecular-field-split 2p levels in H2S

Download: PDF (116 kB) or Buy this Article (Use Article Pack) Export: BibTeX or EndNote (RIS)

André Machado Bueno
Institute of Physics, Brasilia University, Caixa Postal 04455, 70910-900 Brasília-DF, Brazil

Arnaldo Naves de Brito *
Laboratório Nacional de Luz Síncrotron, Box 6192, CEP 13084-971, Campinas, Brazil

Reinhold F. Fink †, Margit Bässler, Olle Björneholm, Florian Burmeister, Raimund Feifel, and Catalin Miron ‡
Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala, Sweden

Stacey L. Sorensen
Department of Synchrotron Radiation Research, Institute of Physics, University of Lund, Box 118, S-221 00 Lund, Sweden

Honghong Wang and Svante Svensson
Department of Physics, Uppsala University, Box 530, S-751 21 Uppsala, Sweden

Received 14 July 2001; published 28 February 2003

Different lifetime broadenings in molecular-field-split 2p core levels in H2S are predicted theoretically and are identified in an experimental investigation of the S 2p Auger electron spectrum. The measurements were performed for the transition to the vibrationally resolved X1A1 ground state of H2S2+. The lifetimes of the 3e1/2 and 5e1/2 levels of the 2p ionized molecule are found to be 64 and 74 meV, respectively. This unambiguous determination of the lifetime difference of 10±1 meV is only possible as the 4e1/2→X1A1(2b1-2) decay channel that overlaps the 5e1/2→X1A1(2b1-2) channel is practically suppressed in Auger decay in H2S. The lifetime difference is confirmed by ab initio calculations. A theoretical analysis shows that it results from the mutual orientation of the core hole in the intermediate states and the valence electron density in the sulfur 3p orbitals. Both are strongly influenced by the chemical bond. Thus the observed effect is the direct result of a fundamental property of molecular electronic structure.


©2003 The American Physical Society

URL: http://link.aps.org/doi/10.1103/PhysRevA.67.022714
DOI: 10.1103/PhysRevA.67.022714
PACS: 33.20.-t, 33.50.Hv, 33.80.Eh

* Corresponding author. On leave from Institute of Physics, Brasilia University. Fax: +551932874632. Email address: Arnaldo@lnls.br
† Also at Theoretical Chemistry, University of Lund, Box 124, S-221 00 Lund, Sweden.
‡ Present address: Laboratoire L.U.R.E., Bâtiment 209D, Center Universitaire Paris-Sud, F-91898 Orsay Cedex, France and Laboratoire Francis Perrin of SPAM/DRECAM, CE. Saclay, 91191-Gif-sur-Yvette, Cedex, France.

[ Abstract  |  Previous article  |  Next article  |  Issue 2 ]