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

Hsin Tsung Chen, Jia Jen Ho

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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).

Original languageEnglish
Pages (from-to)2564-2571
Number of pages8
JournalJournal of Physical Chemistry A
Volume109
Issue number11
DOIs
Publication statusPublished - 2005 Mar 24

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Potential energy surfaces
Energy barriers
adducts
Observation
products
energy
potential energy
analogs
rings

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical investigation of the mechanisms of reaction of NCN with NO and NS. / Chen, Hsin Tsung; Ho, Jia Jen.

In: Journal of Physical Chemistry A, Vol. 109, No. 11, 24.03.2005, p. 2564-2571.

Research output: Contribution to journalArticle

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