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Rotationally resolved photoionization dynamics of hot CO fragmented from OCS

Rotationally resolved photoionization dynamics of hot CO fragmented from OCS
Rotationally resolved photoionization dynamics of hot CO fragmented from OCS
The photoionization dynamics of rotationally hot CO, photodissociated from OCS, have been studied using laser photoelectron spectroscopy via the intermediate B(1)?(+) Rydberg state leading to the X(2)?(+) of the ion. The photodissociation of OCS near 230 nm produces rotationally hot, but vibrationally cold CO (X(1)? (+),N'',v''=0,1) fragments along with S(D-1) atoms. These high rotational levels show photoelectron spectra with a very strong ?N=0 transition and weaker ?N=+/-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 ?v=0, but also off-diagonal, non-Franck-Condon (?v?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(2) ? core.
enhanced multiphoton ionization, photoelectron angular-distributions, rydberg states, diatomic-molecules, carbonyl sulfide, branching ratios, selection-rules, spectroscopy, photodissociation, radiation
0021-9606
2776-2782
Rijs, Anouk M.
22f7de8f-f400-4c92-9324-20c10bf44a90
Backus, Ellen H.G.
724b6ed8-1c2f-480a-8e49-49fcd505010b
de Lange, Cornelis A.
e93f18cf-3dc4-4064-8ec9-7a52c61a6bbd
Janssen, Maurice H.M.
8661edc8-9b14-4127-903f-78af0a0f881b
Westwood, Nicholas P.C.
a05bafd9-8e68-4086-bfb9-9efee46fe49e
Wang, Kwanghsi
2b4576a9-fd11-4ddf-bec9-e35a283e3603
McKoy, Vincent
68113ade-b95e-422e-9196-6834b48f62e0
Rijs, Anouk M.
22f7de8f-f400-4c92-9324-20c10bf44a90
Backus, Ellen H.G.
724b6ed8-1c2f-480a-8e49-49fcd505010b
de Lange, Cornelis A.
e93f18cf-3dc4-4064-8ec9-7a52c61a6bbd
Janssen, Maurice H.M.
8661edc8-9b14-4127-903f-78af0a0f881b
Westwood, Nicholas P.C.
a05bafd9-8e68-4086-bfb9-9efee46fe49e
Wang, Kwanghsi
2b4576a9-fd11-4ddf-bec9-e35a283e3603
McKoy, Vincent
68113ade-b95e-422e-9196-6834b48f62e0

Rijs, Anouk M., Backus, Ellen H.G., de Lange, Cornelis A., Janssen, Maurice H.M., Westwood, Nicholas P.C., Wang, Kwanghsi and McKoy, Vincent (2002) Rotationally resolved photoionization dynamics of hot CO fragmented from OCS. Journal of Chemical Physics, 116 (7), 2776-2782. (doi:10.1063/1.1434993).

Record type: Article

Abstract

The photoionization dynamics of rotationally hot CO, photodissociated from OCS, have been studied using laser photoelectron spectroscopy via the intermediate B(1)?(+) Rydberg state leading to the X(2)?(+) of the ion. The photodissociation of OCS near 230 nm produces rotationally hot, but vibrationally cold CO (X(1)? (+),N'',v''=0,1) fragments along with S(D-1) atoms. These high rotational levels show photoelectron spectra with a very strong ?N=0 transition and weaker ?N=+/-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 ?v=0, but also off-diagonal, non-Franck-Condon (?v?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(2) ? core.

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More information

Published date: 15 February 2002
Keywords: enhanced multiphoton ionization, photoelectron angular-distributions, rydberg states, diatomic-molecules, carbonyl sulfide, branching ratios, selection-rules, spectroscopy, photodissociation, radiation
Organisations: Chemistry

Identifiers

Local EPrints ID: 19844
URI: http://eprints.soton.ac.uk/id/eprint/19844
ISSN: 0021-9606
PURE UUID: acadd8d6-39c9-4b91-b652-7d6dfa7de64e

Catalogue record

Date deposited: 22 Feb 2006
Last modified: 07 Jan 2022 22:04

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Contributors

Author: Anouk M. Rijs
Author: Ellen H.G. Backus
Author: Cornelis A. de Lange
Author: Maurice H.M. Janssen
Author: Nicholas P.C. Westwood
Author: Kwanghsi Wang
Author: Vincent McKoy

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