Theoretical study of the reaction of Ti+ with SCO in gas phase

被引：13

作者：

Dai, Guo-Liang ^{[1
]}

Fan, Kang-Nian ^{[1
]}

机构：

[1] Fudan Univ, Dept Chem, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200433, Peoples R China

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2007年 / 806卷 / 1-3期

基金：

中国国家自然科学基金;

关键词：

DFT theory; potential energy surface; transition-metal; SCO; OXYGEN-TRANSFER REAGENT; (1)SIGMA(+) GROUND-STATE; GUIDED ION-BEAM; 2ND ROW; C-C; CS2; SCS+; YS+; FE+; THERMOCHEMISTRY;

D O I：

10.1016/j.theochem.2006.12.003

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The quartet and doublet potential energy surfaces for the reaction of Ti+ + SCO have been calculated at the UQCISD(T)/6-311+G*// UB3LYP/6-311+G* level of theory. The present results show that the reaction mechanism is insertion-elimination mechanism both along the C-S and C-O bond activation branches, but the C-S bond activation is much more favorable than the C-O bond activation in energy. The minimum energy reaction path is found to involve the spin inversion in the reaction steps. Specifically, the reaction is most likely to proceed through the following steps: Ti-4(+) + SCO -> (4)IM1 -> CP1 -> (2)IM2 -> (TiS+)-Ti-2 + CO. The overall reaction is calculated to be exothermic by 98.2 kJ/mol, which is in good agreement with the available experimental results. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：261 / 268

页数：8

共 52 条

[1] Carbonyl sulfide (OCS) as a sulfur-containing precursor in MOCVD: A study of mixtures of Me(2)Cd and OCS in the gas and solid phases and their use in MOCVD [J].