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Rotationally resolved photoionization dynamics of hot CO fragmented from OCS

Rijs, Anouk M. and Backus, Ellen H. G. and de Lange, Cornelis A. and Janssen, Maurice H. M. and Westwood, Nicholas P. C. and Wang, Kwanghsi and McKoy, Vincent (2002) Rotationally resolved photoionization dynamics of hot CO fragmented from OCS. Journal of Chemical Physics, 116 (7). pp. 2776-2782. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20151027-154127730

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Abstract

The photoionizationdynamics of rotationally hot CO, photodissociated from OCS, have been studied using laser photoelectron spectroscopy via the intermediate B^1Σ^+Rydberg state leading to the X^2Σ^+ of the ion. The photodissociation of OCS near 230 nm produces rotationally hot, but vibrationally cold CO (X^1Σ^+,N″,v″=0,1) fragments along with S (^1D) atoms. These high rotational levels show photoelectron spectra with a very strong ΔN=0 transition and weaker ΔN=±1, ±2, and ±3 transitions. Agreement between measured and calculated spectra is good and suggests that there is significant angular momentum coupling in the photoelectron orbital. In the ionization step not only Δv=0, but also off-diagonal, non-Franck–Condon (Δv≠0) transitions are observed. The intensities of these transitions vary strongly within the region studied and can be explained by the excitation of superexcited Rydberg states with an A^2Π core.


Item Type:Article
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http://dx.doi.org/10.1063/1.1434993DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/116/7/10.1063/1.1434993PublisherArticle
Additional Information:© 2002 American Institute of Physics. (Received 2 April 2001; accepted 21 November 2001) A.M.R. acknowledges the Holland Research School of Molecular Chemistry for a Ph.D. fellowship. C.A.dL. acknowledges very useful discussions with Professor J. M. Dyke and members of his group during a stay in Southampton in the context of the EC Network on Reactive Intermediates. C.A.dL. and A.M.R. acknowledge helpful discussions at the Lisbon meeting of the EC Network on Reactive Intermediates (April 2001), and thank Ing. D. Bebelaar for technical support. This work was supported by a grant from the National Science Foundation.
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Holland Research School of Molecular ChemistryUNSPECIFIED
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Issue or Number:7
Record Number:CaltechAUTHORS:20151027-154127730
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151027-154127730
Official Citation:Rotationally resolved photoionization dynamics of hot CO fragmented from OCS Rijs, Anouk M. and Backus, Ellen H. G. and de Lange, Cornelis A. and Janssen, Maurice H. M. and Westwood, Nicholas P. C. and Wang, Kwanghsi and McKoy, Vincent, The Journal of Chemical Physics, 116, 2776-2782 (2002), DOI:http://dx.doi.org/10.1063/1.1434993
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61602
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:28 Oct 2015 18:39
Last Modified:03 Oct 2019 09:09

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