Article (Scientific journals)
The Appearance of CH3+ Ions from Methyl Halides by resonant photoionization. A translational energy surprisal analysis. Part I. CH3F.
Momigny, J.; Locht, Robert
1996In Chemical Physics, 206, p. 225-236
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Keywords :
Resonant photoionization; He(I), Ne(I); Translational energy; Surprisal analysis; Autoionization; CH3F
Abstract :
[en] A surprisal analysis has been applied to the translational energy distribution (TED) of CH3++F from CH3F giving rise to a new and deeper insight into the dissociation dynamics involved in the process. For both the 16.5 eV and 21.22 eV photon energies used, the direct population at different energy levels of the B2E state of CH3F+ which is radiationlessly coupled to the repulsive CH3F+(A2A1) state, gives rise to wide and negatively surprised total TEDs. At both energies they have to be ascribed to severe limitations in the vibrational excitation of CH3+. Additionally, in the case of 21.22 eV photons, a non-statistical expression has to be used to account for the density of translational states. At both photon energies, the population of the CH3F+ electronic states through autoionization of Rydberg states accounts for (i) the concurrent appearance of TEDs governed by a pure RRKM behavour and (ii) the positively surprised TEDs where the angular momentum conservation plays an important role. At 16.85 eV photon energy the distributions are assigned to CH3F+ (X2E)->CH3+ (X1A'1)+F. At 21.22 eV photon energy, doubly excited electronic states of CH3F+ are assumed to take part and they are correlated with CH3+ (3A")+F channel.
Research center :
Laboratoire de Dynamique Moléculaire
Disciplines :
Chemistry
Author, co-author :
Momigny, J.
Locht, Robert  ;  Université de Liège - ULiège > Département de Chimie (Faculté des sciences) > Laboratoire de Dynamique Moléculaire (Sciences)
Language :
English
Title :
The Appearance of CH3+ Ions from Methyl Halides by resonant photoionization. A translational energy surprisal analysis. Part I. CH3F.
Alternative titles :
[fr] L'apparition des ions CH3+ à partir des halogénures de méthyle par photoionisation résonante. Une analyse de la surprise d'énergie translationnelle. 1ère Partie: CH3F.
Publication date :
1996
Journal title :
Chemical Physics
ISSN :
0301-0104
Publisher :
Elsevier Science, Amsterdam, Netherlands
Volume :
206
Pages :
225-236
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
Fonds de la Recherche Scientifique (Communauté française de Belgique) - FNRS, FRFC Contrat n° 2.4532.95
Commentary :
- PDF-version of Editor's Postprint available on request - Version-pdf du tiré-à-part disponible sur demande
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since 13 November 2008

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