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Non-Franck-Condon Effects Induced by Shape Resonances and Orbital Evolution in Resonance Enhanced Multiphoton Ionization of Small Molecules

Stephens, J. A. and Braunstein, M. and McKoy, V. and Rudolph, H. and Lee, M. T. (1990) Non-Franck-Condon Effects Induced by Shape Resonances and Orbital Evolution in Resonance Enhanced Multiphoton Ionization of Small Molecules. Physica Scripta, 41 (4). pp. 482-486. ISSN 0031-8949. https://resolver.caltech.edu/CaltechAUTHORS:20151124-092306020

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Abstract

We review and discuss some recent resonance enhanced multiphoton ionization (REMPI) studies of small molecules, emphasizing the role that shape resonances and Rydberg orbital evolution play in determining vibrational and rotational ion distributions. Strong non-Franck-Condon effects observed in ion vibrational distributions for REMPI of O_2 via the C ^3Π_g and d ^1Π_g Rydberg states are partially attributed to a σ_u shape resonance, previously observed in ground state photoionization of diatomic molecules. Autoionization of repulsive valence states also induces non-Franck-Condon effects in these REMPI spectra. Significant non-Franck-Condon effects in molecular REMPI spectra also arise from a mechanism associated with rapid evolution of the resonantly populated Rydberg orbital with changing inter-nuclear distance. These effects should be most pronounced in diatomic hydrides, and are illustrated by theoretical predictions of vibrational and rotational ion distributions for REMPI of OH and CH via the D ^2Σ^− and E' ^2Σ^+ Rydberg states, respectively.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1088/0031-8949/41/4/023DOIArticle
http://iopscience.iop.org/article/10.1088/0031-8949/41/4/023/metaPublisherArticle
Additional Information:© 1989 IOP Publishing Ltd. Received July 16, 1989; accepted October 27, 1989. Contributed talk presented at the Ninth International Conference on Vacuum Ultraviolet Radiation Physics, Honolulu, Hawaii, July 17-21, 1989. Contribution No. 7978. The authors are grateful to P. J. Miller and W. A. Chupka for permission to use their unpublished REM PI photoelectron spectra for the 0_2 d ^1n_g, state. This work was supported by grants from the National Science Foundation (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 (DE-FG03-87ER60513). We also acknowledge use of resources of the San Diego SuperComputer Center, which is supported by the National Science Foundation.
Funders:
Funding AgencyGrant Number
NSFCHE-8521391
Air Force Office of Scientific Research (AFOSR)87-0039
Department of Energy (DOE)DE-FG03-87ER60513
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics7978
Issue or Number:4
Record Number:CaltechAUTHORS:20151124-092306020
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151124-092306020
Official Citation:J A Stephens et al 1990 Phys. Scr. 41 482
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:62358
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:24 Nov 2015 17:55
Last Modified:03 Oct 2019 09:18

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