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APS » Journals » Phys. Rev. Lett. » Volume 92 » Issue 14
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Phys. Rev. Lett. 92, 143002 (2004) [4 pages]

Observation of the Symmetry-Forbidden 5σu→kσu CS2 Transition: A Vibrationally Driven Photoionization Resonance

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G. J. Rathbone* and E. D. Poliakoff†
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA

John D. Bozek
Advanced Light Source, Lawrence Berkeley National Laboratory, University of California, Berkeley, California 94720, USA

R. R. Lucchese
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA

Received 18 September 2003; published 8 April 2004

Vibrationally resolved photoelectron spectroscopy and Schwinger calculations are used to characterize a new resonance phenomenon in the 5σu→kσu photoionization of CS2. This resonant channel is symmetry forbidden, yet is observable because it is activated by the antisymmetric stretching vibration. In addition, we show that a Franck-Condon breakdown occurs even though the energy dependence of the cross section is insensitive to geometry changes, which is unprecedented in photoionization.

© 2004 The American Physical Society

URL:
http://link.aps.org/doi/10.1103/PhysRevLett.92.143002
DOI:
10.1103/PhysRevLett.92.143002
PACS:
33.60.Cv, 33.20.Ni, 33.20.Wr, 33.80.Eh

*Current address: JILA, University of Colorado, Boulder, CO 80309-0440, USA.

†Author to whom correspondence should be addressed.

Email address: epoliak@lsu.edu

 
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