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Published July 1, 1991 | Published
Journal Article Open

Rotationally resolved photoelectron spectroscopy of the ^2Σ^− Rydberg states of OH: The role of Cooper minima

Abstract

We have measured rotationally resolved photoelectron spectra of the OH radical using (2+1) resonance enhanced multiphoton ionizationspectroscopy via the D  ^2Σ^−(3pσ) and 3 ^2Σ^−(4sσ) Rydberg states. For the D  ^2Σ^−(3pσ) state, we observe primarily ΔN=even distributions of ionic rotational states, in contrast to the ΔN=odd distribution expected for ionization of a 3pσ Rydberg electron. The observations are described quantitatively by ab initio calculations which predict a Cooper minimum in the 3pσ→kπ(l=2) channel, whose occurrence determines the ΔN=even ion rotational distribution. In contrast, the 3 ^2Σ^−(4sσ) photoelectron spectra reveal a broad distribution in rotational levels, arising from greater l mixing in the higher Rydberg orbital and much weaker Cooper minima in the continuum.

Additional Information

© 1991 American Institute of Physics. (Received 29 March 1991; accepted 30 April 1991) Work at the University of Amsterdam was supported by the Netherlands Organization for Scientific Research (N.W.O). Work at Caltech was supported by grants from the National Science Foundation (Grant No. CHE-8521391), Air Force Office of Scientific Research (Contract No. 87-0039), and the Office of Health and Environmental Research of the U.S. Department of Energy (Grant No. DE-FG03-87ER60513), and resources of the Jet Propulsion Laboratory/Caltech Cray X-MP.

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