Xiao-li Song, Li-guo Gao. C-S Activation of CS2 by Nb+ in Gas Phase[J]. Chinese Journal of Chemical Physics , 2009, 22(3): 297-302. doi: 10.1088/1674-0068/22/03/297-302
Citation: Xiao-li Song, Li-guo Gao. C-S Activation of CS2 by Nb+ in Gas Phase[J]. Chinese Journal of Chemical Physics , 2009, 22(3): 297-302. doi: 10.1088/1674-0068/22/03/297-302

C-S Activation of CS2 by Nb+ in Gas Phase

doi: 10.1088/1674-0068/22/03/297-302
Funds:  In this work we present a DFT study of the reaction of Nb+ with CS2, which is a representative system selected for the reactions of second-row early transition metal ions with CS2. The reaction of Nb+ with CS2 proceeds according to the insertion-elimination mechanism but not the abstraction mechanism. We found that the reaction of Nb+ with CS2 is exothermic by 2.9 kJ/mol. The present calculations support the find-ings of early experiments. ISC between the two surfaces of [Nb, C, S]+ does occur, and the MECP was found.
  • Received Date: 2008-11-22
  • The reaction of Nb+ with CS2, producing cationic transition-metal sulfide and CS, was taken as a representative example to elucidate the overall mechanism of reactions of second-row early transition metal ions with CS2. The reactions in both triplet and quintet state were studied by using the UB3LYP density functional method with the Stuttgart pseudo potentials and corresponding basis sets for Nb+ and the standard 6-311+G(2d) basis sets for C and S. The geometries for reactants, the transition states, and the products were completely optimized. All the transition states were verified by vibrational analysis and intrinsic reaction coordinate calculations. The results show that the reaction mechanism between niobium ion and CS2 is an insertion-elimination mechanism. Intersystem crossing may occur in the reaction Nb+ with CS2 and a minimum energy crossing point was found.
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C-S Activation of CS2 by Nb+ in Gas Phase

doi: 10.1088/1674-0068/22/03/297-302
Funds:  In this work we present a DFT study of the reaction of Nb+ with CS2, which is a representative system selected for the reactions of second-row early transition metal ions with CS2. The reaction of Nb+ with CS2 proceeds according to the insertion-elimination mechanism but not the abstraction mechanism. We found that the reaction of Nb+ with CS2 is exothermic by 2.9 kJ/mol. The present calculations support the find-ings of early experiments. ISC between the two surfaces of [Nb, C, S]+ does occur, and the MECP was found.

Abstract: The reaction of Nb+ with CS2, producing cationic transition-metal sulfide and CS, was taken as a representative example to elucidate the overall mechanism of reactions of second-row early transition metal ions with CS2. The reactions in both triplet and quintet state were studied by using the UB3LYP density functional method with the Stuttgart pseudo potentials and corresponding basis sets for Nb+ and the standard 6-311+G(2d) basis sets for C and S. The geometries for reactants, the transition states, and the products were completely optimized. All the transition states were verified by vibrational analysis and intrinsic reaction coordinate calculations. The results show that the reaction mechanism between niobium ion and CS2 is an insertion-elimination mechanism. Intersystem crossing may occur in the reaction Nb+ with CS2 and a minimum energy crossing point was found.

Xiao-li Song, Li-guo Gao. C-S Activation of CS2 by Nb+ in Gas Phase[J]. Chinese Journal of Chemical Physics , 2009, 22(3): 297-302. doi: 10.1088/1674-0068/22/03/297-302
Citation: Xiao-li Song, Li-guo Gao. C-S Activation of CS2 by Nb+ in Gas Phase[J]. Chinese Journal of Chemical Physics , 2009, 22(3): 297-302. doi: 10.1088/1674-0068/22/03/297-302

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