title: Theoretical study of the reaction mechanism of HCN+ and CH4 of relevance to Titan's ion chemistry.
abstract: Titan is the largest satellite of Saturn. In its atmosphere, CH4 is the most abundant neutral after nitrogen. In this paper, the complex doublet potential-energy surface related to the reaction between HCN+ and CH4 is investigated at the B3LYP/6-311G(d,p), CCSD(T)/6-311G++(3df,2pd)(single-point), and QCISD/6-311G(d,p) computational levels. A total of seven products are located on the PES. The initial association of HCN+ with CH4 is found to be a prereaction complex 1 (HCNHCH3(+)) without barrier. Starting from 1, the most feasible pathway is the direct H-abstraction process (the internal C-H bond dissociation) leading to the product P1 (HCNH++CH3). By C-C addition, prereaction complex 1 can form intermediate 2 (HNCHCH3(+)) and then lead to the product P2 (CH3CNH++H). The rate-controlling step of this process is only 25.6 kcal/mol. It makes the Path P2 (1) R --> 1 --> TS1/2 --> 2 --> TS2/P2 --> P2 another possible way for the reaction. P3 (HCNCH3(+) + H), P5 (cNCHCH2(+) + H2), and P6 (NCCH3(+) + H2) are exothermic products, but they have higher barriers (more than 40.0 kcal/mol); P4 (H + HCN + CH3(+)) and P7 (H + H2 + HCCNH+) are endothermic products. They should be discovered under different experimental or interstellar conditions. The present study may be helpful for investigating the analogous ion-molecule reaction in Titan's atmosphere.
authors.affiliation: State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.forename: Hui-ling
authors.initials: HL
authors.lastname: Liu
authors.forename: Xu-ri
authors.initials: XR
authors.lastname: Huang
authors.forename: Cai-yun
authors.initials: CY
authors.lastname: Geng
authors.forename: Chia-chung
authors.initials: CC
authors.lastname: Sun
authors.forename: Au-chin
authors.initials: AC
authors.lastname: Tang