Theoretical investigation of the mechanisms of reaction of NCN with NO and NS

Hsin Tsung Chen, Jia Jen Ho

研究成果: 雜誌貢獻文章

18 引文 斯高帕斯(Scopus)

摘要

Quantum-chemical calculations were performed on the mechanisms of reaction of NCN with NO and NS. Possible mechanisms were classified according to four pathways yielding products in the following four possible groups: N 2O/N2S + CN, N2 + NCO/NCS, N2 + CNO/CNS, and CNN + NO/NS, labeled in order from pl/pls to p4/p4s. The local structures, transition structures, and potential-energy surfaces with respect to the reaction coordinates are calculated, and the barriers are compared. In the NCN + NO reaction, out of several adduct structures, only the nitroso adduct NCNNO lies lower in energy than the reactants, by 21.89 kcal/mol; that adduct undergoes rapid transformation into the products, in agreement with experimental observation. For the NS counterpart, both thionitroso NCNNS and thiazyl NCNSN adducts have energies much lower than those of the reactants, by 43 and 29 kcal/mol, respectively, and a five-membered-ring NCNNS (having an energy lower than those of the reactants by 36 kcal/mol) acts as a bridge in connecting these two adducts. The net energy barriers leading to product channels other than p4s are negative for the NS reaction, whereas those for the NO analogue are all positive. The channel leading to pi (N2O + CN) has the lowest energy (3.81 kcal/mol), whereas the channels leading to p2 (N2 + NCO) and p2s (N2 + NCS) are the most exothermic (100.94 and 107.38 kcal/mol, respectively).

原文英語
頁(從 - 到)2564-2571
頁數8
期刊Journal of Physical Chemistry A
109
發行號11
DOIs
出版狀態已發佈 - 2005 三月 24

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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