Electronic state dependence of the ion–molecule reaction CH3CN+ + CH3CN → CH4CN+ + CH2CN: threshold electron–secondary ion coincidence (TESICO) and direct ab initio molecular dynamics study

文献情報

出版日 2010-10-26

DOI 10.1039/C004202A

インパクトファクター 3.676

著者

Hiroto Tachikawa, Takahiro Fukuzumi, Kazushige Inaoka, Inosuke Koyano

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要旨

The ion–molecule reaction, CH3CN+ + CH3CN → CH3CNH+ + CH2CN, has been investigated using the threshold electron–secondary ion coincidence (TESICO) technique. Relative reaction cross sections for two microscopic reaction mechanisms, i.e., proton transfer (PT) from the acetonitrile ion CH3CN+ to neutral acetonitrile CH3CN and hydrogen atom abstraction (HA) by CH3CN+ from CH3CN, have been determined for two low-lying electronic states, 2E and 2A1 of the CH3CN+ primary ion. The cross section for PT of the 2A1 state was smaller than that of the 2E state, whereas that of HA are almost the same in the two states. Ab initio calculations showed that the dissociation of the C–H+ bond of CH3CN+ is easier in the 2E state than that in the 2A1 state. The direct ab initio molecular dynamics (MD) calculations showed that two mechanisms, direct proton transfer and complex formation, contribute the reaction dynamics.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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