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Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of Rydberg states of NH

Wang, Kwanghsi and Stephens, J. A. and McKoy, V. and de Beer, E. and de Lange, C. A. and Westwood, N. P. C. (1992) Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of Rydberg states of NH. Journal of Chemical Physics, 97 (1). pp. 211-221. ISSN 0021-9606. doi:10.1063/1.463619. https://resolver.caltech.edu/CaltechAUTHORS:20151028-114737097

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Abstract

Results of combined theoretical and experimental studies of photoelectron spectra resulting from (2+1) resonance enhanced multiphoton ionization (REMPI) via the f ^1Π(3pσ), g ^1Δ(3pπ), and h ^1Σ^+(3pπ) Rydberg states of NH are reported. The overall agreement between these calculated and measured spectra is encouraging. Strong ΔN=N+−N’=even peaks, particularly for ΔN=0, are observed in these spectra. Low‐energy Cooper minima are predicted to occur in the l=2 wave of the kπ(^1Σ^+), kπ(^1Σ^−), and kπ(^1Δ) photoelectron channels for the f state, the kπ(^1Δ), kδ(^1Π), and kδ(^1Φ) channels for the g state, and the kπ(^1Σ^+) and kδ(^1Π) channels for the h state of NH. Depletion of the d wave (l=2) contributions to the photoelectron matrix element in the vicinity of these Cooper minima subsequently enhances the relative importance of the odd l  waves. The observed ΔN transitions are also affected by strong l  mixing in the electronic continuum induced by the nonspherical molecular potential. Interference of continuum waves between degenerate ionization channels also determines the spectral pattern observed for photoionization of the f ^1Π state of NH. Photoelectron angular distributions and the angular momentum compositions of photoelectron matrix elements provide further insight into the origin of these Cooper minima.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1063/1.463619DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/97/1/10.1063/1.463619PublisherArticle
Additional Information:© 1992 American Institute of Physics. (Received 20 February 1992; accepted 17 March 1992) Work at the California Institute of Technology was supported by grants from the National Science Foundation, Air Force Office of Scientific Research, and the Office of Health and Environmental Research of the U.S. Department of Energy. We acknowledge use of resources of the Jet Propulsion Laboratory/Caltech CRAY Y-MP2E/116 Supercomputer. Work at the University of Amsterdam was supported by the Netherlands Organization for Scientific Research (N.W.O.).
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Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO)UNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics8577
Issue or Number:1
DOI:10.1063/1.463619
Record Number:CaltechAUTHORS:20151028-114737097
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151028-114737097
Official Citation:Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of Rydberg states of NH Wang, Kwanghsi and Stephens, J. A. and McKoy, V. and de Beer, E. and de Lange, C. A. and Westwood, N. P. C., The Journal of Chemical Physics, 97, 211-221 (1992), DOI:http://dx.doi.org/10.1063/1.463619
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61665
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:30 Oct 2015 15:17
Last Modified:10 Nov 2021 22:52

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