Theoretical study of the CH3 + NS and related reactions: mechanism of HCN formation |
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| Authors: | TRUNG NGOC LE LOC THANH NGUYEN MINH THO NGUYEN |
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| Institution: | 1. Department of Chemistry , University of Leuven , Celestijnenlaan 200F, B-3001, Leuven, Belgium;2. Faculty of Chemistry , University of Danang , Vietnam;3. Faculty of Chemical Engineering , HoChiMinh City University of Technology , Vietnam;4. Department of Chemistry , University of Leuven , Celestijnenlaan 200F, B-3001, Leuven, Belgium |
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| Abstract: | More than thirty equilibrium and transition structures on the CH3NS] potential energy surface have been located using the B3LYP/6-311 + + G(d,p) method. Thioformaldoxime (3) turns out to be the most stable isomer followed by thionitrone (2), a three-membered ring, thionitrosyl methane (1) and thiazyl methane. These isomers are connected to each other by 1,2H and 1,3H shifts and ring—chain rearrangement, but the associated energy barriers are rather high, making most of them stable with respect to unimolecular transformations. Starting from CH3 + NS, a possible initial atmospheric reaction, HCN formation appears to be the most favoured process through a cascade involvement of 1, 2 and 3. The standard heats of formation, ΔH 0 f,298 are calculated to be: 3, 149kJmol?1; and 1, 218kJmol?1; using the CCSD(T)/6-311+ +G(3df,2p) method, with an error of ±10kJ mol?1. |
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