Journal of the Chemical Society. Faraday transactions vol:94 issue:24 pages:3541-3547
date:Univ Louvain, Dept Chem, B-3001 Louvain, Belgium; HoChiMinh City Univ Technol, Fac Chem Engn, Thanh Pho Ho Chi Minh, Vietnam; Univ Danang, Fac Chem, Danang, Vietnam
The potential-energy surface related to the H2N + NS reaction, which involves 13 intermediates and fragment products, as well as 14 transition structures has been fully characterized using both molecular orbital (MP2) and density functional theory (B3LYP) and the 6-311+ +G(d,p) basis set. Improved electronic energies have also been obtained using single-point coupled-cluster CCSD(T) calculations. The system is shown to have three different groups of products: N2H + SH, N2S + H-2 and N-2 + H2S and a rather complex reaction mechanism. Starting from H2N + NS, several low-lying [H2N2S] isomers participate in the elimination of H-2 and N-2. The N-2 elimination appears to be favoured over other reaction channels in the destruction of NS. The standard enthalpies of formation of the most stable isomers have been estimated, Delta(f)H(298)(degrees), in kJ mol(-1): H2N-N=S: 250, H2N-S drop N: 262, NH=NH=S: 264, NH=N-SH :247 and NH=S=NH: 318.