| COS Activation by Zr~＋ in the Gas Phase：A Case of Two-state Reactivity Process |
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| 引用本文： | 余仕问,侯能帮,缪应纯,林雪飞,杨思娅,谢小光.COS Activation by Zr~＋ in the Gas Phase：A Case of Two-state Reactivity Process[J].结构化学,2011,30(2):216-224. |
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| 作者姓名： | 余仕问 侯能帮 缪应纯 林雪飞 杨思娅 谢小光 |
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| 作者单位： | School of Chemistry and Chemical Engineering;Qujing Normal University;Department of Chemistry;Yunnan University; |
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| 基金项目： | 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) |
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| 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.
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| 关 键 词： | 反应过程 氧化锆 COS 活化 气相 B3LYP 反应机制 密度泛函方法 |
COS Activation by Zr+ in the Gas Phase: A Case of Two-state Reactivity Process |
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| YU Shi-Wen,HOU Neng-Bang,MIAO Ying-Chun,LIN Xue-Fei,YANG Si-Ya,XIE Xiao-Guang.COS Activation by Zr+ in the Gas Phase: A Case of Two-state Reactivity Process[J].Chinese Journal of Structural Chemistry,2011,30(2):216-224. |
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| Authors: | YU Shi-Wen HOU Neng-Bang MIAO Ying-Chun LIN Xue-Fei YANG Si-Ya XIE Xiao-Guang |
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| Institution: | YU Shi-Wen a HOU Neng-Bang a MIAO Ying-Chun a LIN Xue-Fei a YANG Si-Ya a XIE Xiao-Guang b② a (School of Chemistry and Chemical Engineering,Qujing Normal University,Qujing 655011,China) b (Department of Chemistry,Yunnan University,Kunming 650091,China) |
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| Abstract: | 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 inserti... |
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| Keywords: | zirconium cation COS reaction mechanism DFT CCSD (T) |
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