Rotational energy transfer and rotationally specific vibration–vibration intradyad transfer in collisions of C2H2 1g+(31/214151, J=10) with C2H2, Ar, He and H2

Hdl Handle:
http://hdl.handle.net/10149/98580
Title:
Rotational energy transfer and rotationally specific vibration–vibration intradyad transfer in collisions of C2H2 1g+(31/214151, J=10) with C2H2, Ar, He and H2
Authors:
Henton, S. (Sarah); Islam, M. (Meezanul); Gatenby, S. (Simon); Smith, I. W. M. (Ian)
Affiliation:
The University of Birmingham. School of Chemistry.
Citation:
Henton, S. et. al. (1998) 'Rotational energy transfer and rotationally specific vibration–vibration intradyad transfer in collisions of C2H2 1g+(31/214151, J=10) with C2H2, Ar, He and H2', Journal of the Chemical Society Faraday Transactions, 94 (21), pp.3219-3228.
Publisher:
Royal Society of Chemistry
Journal:
Journal of the Chemical Society Faraday Transactions
Issue Date:
7-Nov-1998
URI:
http://hdl.handle.net/10149/98580
DOI:
10.1039/a805898i
Abstract:
Infrared-ultraviolet double resonance (IRUVDR) experiments have been performed on samples of pure C2H2 and on C2H2 diluted in Ar, He and H2. Pulses of tunable IR radiation from an optical parametric oscillator (OPO) excited molecules of C2H2 to the J = 10 rotational level of the lower component state (II) of the (31/214151)II Fermi dyad in the X̃ 1Σg+ electronic ground state of C2H2 and tunable UV radiation was used to record laser-induced spectra at short delays. In this way, state-to-state rate coefficients have been determined for two kinds of processes:§ (a) rotational energy transfer (RET) induced by collisions with C2H2, Ar, He and H2 from the initial level Ji = 10 to other levels (Jf = 2-8, 12-20) within the same component (II) of the (31/214151) Fermi dyad, and (b) intradyad transfer in C2H2-C2H2 collisions to specific levels (Jf = 2-14, 18) in the other component (I) of this Fermi dyad. Transfer from II to I is found to account for ca. 16% of the total relaxation from (II, Ji = 10). The distribution of state-to-state rate coefficients for RET becomes broader as the mass of the collision partner increases, in accord with the predictions of a simple classical model. Absolute values of the state-to-state rate coefficients are determined by scaling the results to the previously determined rate coefficients for rotational relaxation by the same collision partner. It is suggested that intradyad transfer is relatively facile because of the difference in the two diagonal terms in the vibrational matrix element for the transition, with the 〈214151|V|21415 1〉 component being larger than the 〈31|V|31〉 component.
Type:
Article
Language:
en
Keywords:
Rotational energy transfer; Infrared-ultraviolet double resonance; C2H2; state-to-state rate coefficients
ISSN:
0956-5000; 1364-5455
Rights:
Author can archive publisher's version/PDF. For full details see http://www.sherpa.ac.uk/romeo/ [Accessed 12/05/2010]
Citation Count:
2 [Scopus, 12/05/2010]

Full metadata record

DC FieldValue Language
dc.contributor.authorHenton, S. (Sarah)en
dc.contributor.authorIslam, M. (Meezanul)en
dc.contributor.authorGatenby, S. (Simon)en
dc.contributor.authorSmith, I. W. M. (Ian)en
dc.date.accessioned2010-05-12T09:42:18Z-
dc.date.available2010-05-12T09:42:18Z-
dc.date.issued1998-11-07-
dc.identifier.citationJournal of the Chemical Society Faraday Transactions; 94(21):3219-3228en
dc.identifier.issn0956-5000-
dc.identifier.issn1364-5455-
dc.identifier.doi10.1039/a805898i-
dc.identifier.urihttp://hdl.handle.net/10149/98580-
dc.description.abstractInfrared-ultraviolet double resonance (IRUVDR) experiments have been performed on samples of pure C2H2 and on C2H2 diluted in Ar, He and H2. Pulses of tunable IR radiation from an optical parametric oscillator (OPO) excited molecules of C2H2 to the J = 10 rotational level of the lower component state (II) of the (31/214151)II Fermi dyad in the X̃ 1Σg+ electronic ground state of C2H2 and tunable UV radiation was used to record laser-induced spectra at short delays. In this way, state-to-state rate coefficients have been determined for two kinds of processes:§ (a) rotational energy transfer (RET) induced by collisions with C2H2, Ar, He and H2 from the initial level Ji = 10 to other levels (Jf = 2-8, 12-20) within the same component (II) of the (31/214151) Fermi dyad, and (b) intradyad transfer in C2H2-C2H2 collisions to specific levels (Jf = 2-14, 18) in the other component (I) of this Fermi dyad. Transfer from II to I is found to account for ca. 16% of the total relaxation from (II, Ji = 10). The distribution of state-to-state rate coefficients for RET becomes broader as the mass of the collision partner increases, in accord with the predictions of a simple classical model. Absolute values of the state-to-state rate coefficients are determined by scaling the results to the previously determined rate coefficients for rotational relaxation by the same collision partner. It is suggested that intradyad transfer is relatively facile because of the difference in the two diagonal terms in the vibrational matrix element for the transition, with the 〈214151|V|21415 1〉 component being larger than the 〈31|V|31〉 component.en
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.rightsAuthor can archive publisher's version/PDF. For full details see http://www.sherpa.ac.uk/romeo/ [Accessed 12/05/2010]en
dc.subjectRotational energy transferen
dc.subjectInfrared-ultraviolet double resonanceen
dc.subjectC2H2en
dc.subjectstate-to-state rate coefficientsen
dc.titleRotational energy transfer and rotationally specific vibration–vibration intradyad transfer in collisions of C2H2 1g+(31/214151, J=10) with C2H2, Ar, He and H2en
dc.typeArticleen
dc.contributor.departmentThe University of Birmingham. School of Chemistry.en
dc.identifier.journalJournal of the Chemical Society Faraday Transactionsen
ref.citationcount2 [Scopus, 12/05/2010]en
or.citation.harvardHenton, S. et. al. (1998) 'Rotational energy transfer and rotationally specific vibration–vibration intradyad transfer in collisions of C2H2 1g+(31/214151, J=10) with C2H2, Ar, He and H2', Journal of the Chemical Society Faraday Transactions, 94 (21), pp.3219-3228.-
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