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Title: Nucleophilic substitution with two reactive centers: The CN{sup −} + CH{sub 3}I case

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4934993· OSTI ID:22493223
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  1. Department of Physics, AlbaNova, Stockholm University, 10691 Stockholm (Sweden)

The nucleophilic substitution reaction CN{sup −} + CH{sub 3}I allows for two possible reactive approaches of the reactant ion onto the methyl halide, which lead to two different product isomers. Stationary point calculations predict a similar shape of the potential and a dominant collinear approach for both attacks. In addition, an H-bonded pre-reaction complex is identified as a possible intermediate structure. Submerged potential energy barriers hint at a statistical formation process of both CNCH{sub 3} and NCCH{sub 3} isomers at the experimental collision energies. Experimental angle- and energy differential cross sections show dominant direct rebound dynamics and high internal excitation of the neutral product. No distinct bimodal distributions can be extracted from the velocity images, which impedes the indication of a specific preference towards any of the product isomers. A forward scattering simulation based on the experimental parameters describes accurately the experimental outcome and shows how the possibility to discriminate between the two isomers is mainly hindered by the large product internal excitation.

OSTI ID:
22493223
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 18; Other Information: (c) 2015 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English