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Dissociative recombination of fully deuterated protonated acetonitrile, CD3CND+: Product branching fractions, absolute cross section and thermal rate coefficient
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
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2008 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 10, no 27, 4014-4019 p.Article in journal (Refereed) Published
Abstract [en]

The dissociative recombination of fully deuterated protonated acetonitrile, CD3CND+, has been investigated at the CRYRING heavy ion storage ring, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Branching fractions were measured at similar to 0 eV relative collision energy between the ions and the electrons and in 65% of the DR events there was no rupture of bonds between heavy atoms. In the remaining 35%, one of the bonds between the heavy atoms was broken. The DR cross-section was measured between similar to 0 eV and 1 eV relative collision energy. In the energy region between 1 meV and 0.1 eV the cross section data were best fitted by the expression sigma = 7.37 x 10(-16) (E/eV)(-1.23) cm(2), whereas sigma = 4.12 x 10(-16) (E/eV)(-1.46) cm(2) was the best fit for the energy region between 0.1 and 1.0 eV. From the cross section a thermal rate coefficient of alpha(T) = 8.13 x 10(-7) (T/300)(-0.69) cm(3) s(-1) was deduced.

Place, publisher, year, edition, pages
2008. Vol. 10, no 27, 4014-4019 p.
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-43002DOI: 10.1039/b801566jISI: 000257425100006OAI: oai:DiVA.org:su-43002DiVA: diva2:352899
Available from: 2010-09-23 Created: 2010-09-23 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Dissociative recombination of organic molecular ions of relevance for interstellar clouds and Titan's upper atmosphere
Open this publication in new window or tab >>Dissociative recombination of organic molecular ions of relevance for interstellar clouds and Titan's upper atmosphere
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis presents experimental studies on the dissociative recombination (DR) of the organic molecular ions CD3CND+, CH2CHCNH+, CH3CH2CNH+, CD3CDO+, CH3CHO+ and DCOOD2+. The experiments were all performed at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. DR is the process in which a singly charged molecular cation captures a free electron, forming a highly excited intermediate molecule which then dissociates into exclusively neutral fragments. The process plays an important role as a plasma neutralizing mechanism in many cold, low density plasmas such as those encountered in planetary ionospheres and interstellar clouds. DR can also act as the final step in the gas-phase synthesis of different neutral molecules in such environments.

Our experimental findings indicate that nitriles that are lost by protonation in Titan’s upper atmosphere or in interstellar clouds to a large extent may be recycled by DR. Also, it appears that the DR of nitrile ions does not break the C-N bond, which supports the hypothesis that nitriles which are formed in Titan’s upper atmosphere do not degrade to recover N2. For the studied acetaldehyde cations, CD3CDO+ and CH3CHO+, we observed a considerable isotopic effect in the cross section, with the lighter isotopologue being more reactive. In the DR of DCOOD2+ an upper limit of only 13% for the branching fraction of the DCOOD + D channel was found. This finding has pronounced effects on the predicted abundance of formic acid in dark clouds.

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University, 2010. 70 p.
Keyword
Dissociative recombination, Astrochemistry
National Category
Physical Sciences
Research subject
Chemical Physics
Identifiers
urn:nbn:se:su:diva-43372 (URN)978-91-7447-133-5 (ISBN)
Public defence
2010-11-26, sal FB42, AlbaNova Universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00 (English)
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Available from: 2010-11-03 Created: 2010-10-11 Last updated: 2010-10-26Bibliographically approved

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Vigren, ErikHamberg, MathiasZhaunerchyk, VitaliThomas, Richard D.Larsson, MatsGeppert, Wolf D.
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