Orientation dependence of the reaction of K + CH 3CN

• Published in: Chemical physics letters Vol. 373; no. 5; pp. 586 - 590
• Main Author: Maclagan, Robert G.A.R.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 2003
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/S0009-2614(03)00652-3

Calculations are reported at the MP2/6-311++G(2df,2pd) level of theory on the reaction of K atoms with CH 3CN, with different orientations of the CH 3CN molecule with respect to the incoming K atom. Approach along a minimum energy pathway does not involve a simple harpoon mechanism. Stretching of the C–C bond of CH 3CN facilitates electron transfer. Electron transfer occurs on a repulsive surface for CN end approach and on an attractive surface for methyl end approach. For approach from the methyl end of the molecule, the barrier to the formation of CH 2CN − is lower than that for the formation of CH 3CN − or CN − as the K atom approaches closer to the CH 3CN molecule.