文献类型：期刊文献

英文题名：Theoretical investigation on acetylene cyclotrimerization catalysed by TiO₂ and Ti

作者：Deng, Zhe-Peng[1,2];Wang, Yong-Cheng[1];Mou, Dan[3];Sun, Yu[4];Da, Hu[2];Gao, Jian-De[5]

第一作者：Deng, Zhe-Peng

通信作者：Wang, YC[1]

机构：[1]Northwest Normal Univ, Coll Chem & Chem Engn, Lanzhou 730070, Gansu, Peoples R China;[2]Gansu Comp Ctr, Running Maintenance Dept, Lanzhou, Gansu, Peoples R China;[3]1 Middle Sch, Huining, Huining County, Peoples R China;[4]Northwest Univ Nationalities, Expt Ctr, Lanzhou, Gansu, Peoples R China;[5]Gansu Univ Chinese Med, Lanzhou, Gansu, Peoples R China

第一机构：Northwest Normal Univ, Coll Chem & Chem Engn, Lanzhou 730070, Gansu, Peoples R China

通信机构：[1]corresponding author), Northwest Normal Univ, Coll Chem & Chem Engn, Lanzhou 730070, Gansu, Peoples R China.

年份：2019

卷号：32

期号：5

外文期刊名：JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000465024000001)】；

基金：National Natural Science Foundation of China, Grant/Award Number: 21263023; Youth Science Foundation of Gansu Province, Grant/Award Number: 17JR5RA282; Central Universities Fundamental Research Foundation, Grant/Award Number: 31920160055; Natural Science Foundation of Gansu Province, Grant/Award Numbers: 1606RJZA209 and 17JR5RA172

语种：英文

外文关键词：alkynes; cyclotrimerization; density functional theory; kinetics; spin crossover

摘要：The reaction mechanisms for acetylene cyclotrimerization using TiO2 and Ti catalysts were studied by the density functional theory (DFT) method. Interestingly, the reaction catalysed by TiO2 occurs on the potential energy surface (PES) with a singlet state. For the same reaction catalysed by Ti, spin-orbit coupling (SOC) calculations were performed to discuss spin inversion between the triplet and singlet PESs. The chance that an electron hops in the vicinity of the minimum-energy crossing point (MECP) was verified regarding the Landau-Zener model. The possibilities of single (P1ISC) and double (P2ISC) at MECP1 (SOC = 253.38 cm(-1)) are about 0.35 and 0.46, respectively. The energetic span model developed by Kozuch was applied in the above reactions. The turnover frequency (TOF)-determining transition state (TDTS) and TOF-determining intermediate (TDI) were verified. The TOF value indicates that Ti is a more active catalyst compared with TiO2 in C2H2 cyclotrimerization.