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 ...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.展开更多
基金国家重点研发计划(2021YFA1502400)国家自然科学基金(22272176,22002166,22125205,22072146,22002158)+2 种基金中国科学院洁净能源创新研究院合作基金(DNL202007)榆林学院-中国科学院洁净能源创新研究院联合基金(YLU-DNL Fund 2022008)中国科学院青年创新促进计划(Y201938)资助项目。
文摘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.
