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Studies of valence shell photoionization of Cl_2

Braunstein, M. and McKoy, V. (1990) Studies of valence shell photoionization of Cl_2. Journal of Chemical Physics, 92 (8). pp. 4887-4892. ISSN 0021-9606. doi:10.1063/1.457705.

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We report photoionization cross sections and photoelectron angular distributions for the 5σ_g , 2π_u and 2π_g orbitals of Cl_2 from threshold to ∼20 eV photoelectron energy obtained using Hartree–Fock photoelectron orbitals. These studies were motivated by recent (2+1) resonance enhanced multiphoton ionization (REMPI) experiments via the 2 ^1Π_g (2π^3_g 4sσ_g ) state which show strong non‐Franck–Condon effects in the ion vibrational distribution suggesting that shape and/or autoionizing resonances may play a role near threshold. Previous single‐photon experiments on the valence orbitals of Cl_2 do not give a consistent picture of these cross sections at low energies. Our results show that there is a shape resonance in the kπ_u continuum. However, preliminary studies show that these π_u cross sections have almost no dependence on internuclear distance and could not be the cause of non‐Franck–Condon effects observed in the REMPI experiments.

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Alternate Title:Studies of valence shell photoionization of Cl2
Additional Information:© 1990 American Institute of Physics. (Received 16 October 1989; accepted 4 January 1990) This work was supported by a grant from the National Science Foundation (CHE-8521391). We also acknowledge use of resources of the San Diego SuperComputer Center, which is supported by the National Science Foundation, and the Air Force SuperComputer Center-Kirtland. One of us (M.B.) would like to acknowledge support from a Department of Education Graduate Fellowship and would also like to thank Dr. J. A. Stephens for providing data on atomic chlorine phase shifts.
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Air Force SuperComputer Center-KirtlandUNSPECIFIED
Department of Education Graduate FellowshipUNSPECIFIED
Issue or Number:8
Record Number:CaltechAUTHORS:20151028-114731057
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Official Citation:Studies of valence shell photoionization of Cl2 Braunstein, M. and McKoy, V., The Journal of Chemical Physics, 92, 4887-4892 (1990), DOI:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61643
Deposited By: George Porter
Deposited On:10 Nov 2015 16:12
Last Modified:10 Nov 2021 22:51

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