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

Literature Information

Publication Date 2010-10-26
DOI 10.1039/C004202A
Impact Factor 3.676
Authors

Hiroto Tachikawa, Takahiro Fukuzumi, Kazushige Inaoka, Inosuke Koyano


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Abstract

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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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