COS Activation by Zr^+ in the Gas Phase:A Case of Two-state Reactivity Process  

作　　者：余仕问 侯能帮 缪应纯 林雪飞 杨思娅 谢小光 

机构地区：[1]School of Chemistry and Chemical Engineering,Qujing Normal University [2]Department of Chemistry,Yunnan University

出　　处：《Chinese Journal of Structural Chemistry》2011年第2期216-224,共9页结构化学（英文）

基　　金：Suppoted by the Science Foundation of Qujing Normal School (No. 2008QN004);the Scientific Research Fund of Yunnan Provincial Education (No. 09C0187);the Scientific Research Fund of Yunnan Provincial Education (No. 09Y0392)

摘　　要：To elucidate the mechanisms of Zr ＋ reacting with COS,both the quartet and doublet potential energy surfaces （PESs） for reactions of Zr ＋ （4 F,2 D） with COS in the gas phase have been investigated in detail by means of density functional method （B3LYP）.To obtain more accurate results,the coupled cluster single-point calculations （CCSD（T）） using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr ＋.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr ＋ to yield ZrO ＋ is spin-forbidden （Zr ＋ （4 F） ＋ COS （1 Σ） → ZrO ＋ （2） ＋ CS （1 Σ）） and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.To elucidate the mechanisms of Zr ＋ reacting with COS,both the quartet and doublet potential energy surfaces （PESs） for reactions of Zr ＋ （4 F,2 D） with COS in the gas phase have been investigated in detail by means of density functional method （B3LYP）.To obtain more accurate results,the coupled cluster single-point calculations （CCSD（T）） using B3LYP optimized geometries were performed.For the C-O bond activation,the calculated results indicate that both the quartet and doublet states proceed via an insertion-elimination mechanism.For the C-S bond activation,the quartet reaction has an insertion-elimination mechanism,but the doublet reaction is a direct abstraction of the sulfur atom by Zr ＋.The C-S bond activation is found to be energetically more favorable than the C-O bond activation.It is found that the reaction of the 4 F gound state of Zr ＋ to yield ZrO ＋ is spin-forbidden （Zr ＋ （4 F） ＋ COS （1 Σ） → ZrO ＋ （2） ＋ CS （1 Σ）） and the crossing points were approximately determined.All the results have been compared with the existing experimental and theoretical data.

关 键 词：zirconium cation COS reaction mechanism DFT CCSD （T） 

分 类 号：O611.3[理学—无机化学]