Theoretical Study of the Acetonitrile Reaction with the Methine Radical
L. I. Krikunova1,2, A. A. Kuznetsova1,2, D. P. Porfiriev1,2, V. N. Azyazov2, A. M. Mebel3
1Samara State Aerospace University, Samara, Russia
2Samara Department of the Lebedev Physical Institute, Russian Academy of Sciences, Samara, Russia
3Florida International University, Florida, USA
Keywords: acetonitrile, methine radical, nitriles, quantum chemistry, Density functional theory, coupled cluster method, potential energy surface
Abstract
Results of a theoretical study of the methine radical (CH) with acetonitrile (CH3CN), which is a potentially important step in the formation of heterocyclic nitrogen-containing molecules in the interstellar space and planetary atmospheres, are presented. A profile of the potential energy surface is constructed, which describes the mechanism of the formation of both linear and cyclic products. The geometry, frequency of oscillations, and relative energy of the resultant structures are determined with the use of the explicitly correlated coupled cluster method and the density functional theory CCSD(T)-F12/cc-pVTZ-f12//ωB97xd/cc-pVTZ. Within the framework of the Rice-Ramsperger-Kassel-Marcus theory, rate constants and branching coefficients of reaction products are calculated under the conditions of deep space corresponding to the limit of zero pressure for various impact energies. It is found that the relative yields of reaction products depend on the initial adduct of the reaction.
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