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. doi:10.1063/1.458511. 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.
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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August 1989; accepted 26 January 1990) The authors are grateful to P. J. Miller and W. A. Chupka for permission to use unpublished REMPI photoelectron spectra for the O_2 d ^1Π_g state in this work.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. | ||||||||||
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Issue or Number: | 9 | ||||||||||
DOI: | 10.1063/1.458511 | ||||||||||
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: | 10 Nov 2021 22:51 |
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