Rudolph, H. and Stephens, J. A. and McKoy, V. and Lee, M.-T. (1989) Vibrational state dependence of ionic rotational branching ratios in resonance enhanced multiphoton ionization of CH. Journal of Chemical Physics, 91 (2). pp. 1374-1376. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120524-134812860
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We show that rapid evolution of a Rydberg orbital with internuclear distance in a resonance enhanced multiphoton ionization (REMPI) process can have a profound influence on the production of molecular ions in alternative rotational states. This is illustrated by calculations of ionic rotational branching ratios for (2+1′) REMPI via the O11 (20.5) branch of the E′ ^2Σ^+(3pσ) Rydberg state of CH. The rotational propensity rule for ionization changes from ΔN=odd (ΔN=N_+−N_i) at lower vibrational excitation, as expected from the ΔN+l=odd selection rule, to ΔN=even at higher vibrational levels. This effect is expected to be quite general and should be most readily observable in diatomic hydrides.
|Additional Information:||© 1989 American Institute of Physics. Received 25 April 1989; accepted 12 May 1989. We would like to thank Professor W. Chupka for several helpful discussions. We acknowledge support 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). We also made use of resources of the San Diego SuperComputer Center, which is supported by the National Science Foundation. H. R. gratefully acknowledges support from the NATO Science Fellowship Programme (Denmark).|
|Subject Keywords:||Vibrartional states, Rotational states, Photoionization, Multi-photon processes, Resonance, Enhancement, Branching ratio, Energy dependence, Mehtylene radicals|
|Classification Code:||PACS: 33.80.Rv; 33.20.Vq|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||24 May 2012 22:20|
|Last Modified:||26 Dec 2012 15:15|
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