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Reaction of propionitrile with methylidyne: A theoretical study
Authors:Lubov I Krikunova  Anatoliy A Nikolayev  Denis P Porfiriev  Alexander M Mebel
Institution:1. Samara National Research University, Samara, Russia

Lebedev Physical Institute Samara Branch, Samara, Russia;2. Samara National Research University, Samara, Russia;3. Department of Chemistry and Biochemistry, Florida International University, Miami, Florida, USA

Abstract:The results of a CCSD(T)-F12/cc-pVTZ-f12//ωB97XD/cc-pVTZ quantum-chemical study of the potential energy surface (PES) for the reaction of propionitrile with methylidyne are combined with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the reaction rate constants and product branching ratios in the deep space conditions corresponding to the zero-pressure limit at various collision energies. The most energetically favorable reaction pathways have been identified. The reaction outcome has been shown to strongly depend on the branching in the entrance reaction channel, between CH additions and insertions into various C-H and C-C bonds. For instance, CH addition to the N atom predominantly leads to 3H-pyrrole + H (p9), with CH2NC + C2H4 (p2) also being a significant product. CH addition to the triple C≡N bond mostly results in 2-methylene-2H-azirine + CH3 (p13), whereas CH insertions into C-H bonds in the CH3 and CH2 groups of propionitrile form CH2CN + C2H4 (p1) and CH2CHCN + CH3 (p7) respectively. Less likely CH insertions into single C-C bonds yield CH3CHCHCN + H (p5) and CH2CHCH2CN + H (p8). The results indicate that the methylidyne + propionitrile reaction may represent a critical step toward the formation of heterocyclic N-containing molecules in the interstellar medium and in planetary atmospheres.
Keywords:density functional theory  methylidyne  potential energy surface  propionitrile  pyrrole  quantum chemistry  rate constants
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