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Multiplet-specific shape resonance and autoionization effects in (2+1) resonance enhanced multiphoton ionization of O_2 via the d ^1Π_g state

Stephens, J. A. and Braunstein, M. and McKoy, V. (1990) Multiplet-specific shape resonance and autoionization effects in (2+1) resonance enhanced multiphoton ionization of O_2 via the d ^1Π_g state. Journal of Chemical Physics, 92 (9). pp. 5319-5327. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20151028-114730778

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Abstract

In this paper we discuss the single‐photon ionization dynamics of the d  ^1Π_g Rydberg state of O_2. Comparison is made with vibrationally resolved measurements of photoelectron spectra which employ (2+1) resonance enhanced multiphoton ionization (REMPI) through the d  ^1Π_g state. A σ_u shape resonance near the ionization threshold leads to non‐Franck–Condon vibrational branching ratios and a substantial dependence of photoelectron angular distributions on the vibrational state of the X  ^2Π_g ion. Significant differences exist between our one‐electron predictions and experiment. These are mainly attributed to electronic autoionization of repulsive ^1∑^−_u , ^1∑^+_u , and ^1Δ_u states associated with the 1π^3_u 1π^3_g configuration. A proposed singlet "K" ^1Π_u Rydberg state converging to the A  ^2Π_u ion probably also contributes to autoionization in the d  ^1Π_g state spectrum. We also show that autoionizing H and J  ^3Π_u Rydberg states of O_2 converging to the a  ^4Π_u and A  ^2Π_u ionic thresholds, respectively, may play a previously unsuspected role in the C  ^3Π_g state one‐color REMPI spectra. We discuss multiplet‐specific (spin‐dependent) effects via comparison of these results with recent experimental and theoretical studies of O_2 C  ^3Π_g photoionization.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.458511DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/92/9/10.1063/1.458511PublisherArticle
Alternate Title:Multiplet-specific shape resonance and autoionization effects in (2+1) resonance enhanced multiphoton ionization of O2 via the d 1Πg state
Additional Information:© 1990 American Institute of Physics. (Received 9 August 1989; accepted 26 January 1990) The authors are grateful to P. J. Miller and W. A. Chupka for permission to use unpublished REMPI photoelectron spectra for the O_2 d ^1Π_g state in this work. 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. One of us (M. B.) would like to acknowledge support from a Department of Education Fellowship.
Funders:
Funding AgencyGrant Number
NSFCHE-8521391
Air Force Office of Scientific Research (AFOSR)87-0039
Department of Energy (DOE)DE-FG03-87ER60513
Department of Education FellowshipUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics8015
Issue or Number:9
Record Number:CaltechAUTHORS:20151028-114730778
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151028-114730778
Official Citation:Multiplet‐specific shape resonance and autoionization effects in (2+1) resonance enhanced multiphoton ionization of O2 via the d  1Πg state Stephens, J. A. and Braunstein, M. and McKoy, V., The Journal of Chemical Physics, 92, 5319-5327 (1990), DOI:http://dx.doi.org/10.1063/1.458511
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61642
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:10 Nov 2015 16:31
Last Modified:03 Oct 2019 09:10

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