Theoretical study on the reaction of Nb⁺ with COS in the gas phase

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• 作者：Shiwen Yu ; Taohong Li ; Xuefei Lin ; Siya Yang ; Chengke Sun ; Xiaoguang Xie
• 关键词：Niobium cation ; COS ; Reaction mechanism ; B3LYP ; CCSD(T)
• 刊名：Journal of Molecular Structure: THEOCHEM
• 出版年：2010
• 出版时间：15 August 2010
• 年：2010
• 卷：953
• 期：1-3
• 页码：39-46
• 全文大小：589 K

文摘

The reaction mechanism of Nb⁺ (⁵D, ³P, ¹S) with COS has been investigated in detail by means of density functional method (B3LYP). To obtain an accurate evaluation of the activation barrier and reaction energy, the coupled cluster single-point calculations (CCSD(T)) using the B3LYP structures are performed. The calculated results indicate that the CS bond activation has two different mechanisms, one is an insertion–elimination mechanism, the other is directly abstraction S atom mechanism. The CO bond activation proceeds via an insertion–elimination mechanism. The CS bond activation is found to be energetically much more favorable than the CO bond activation. The Nb⁺(⁵D)+ COS(¹Σ) → NbS⁺(³Σ⁻) + CO(¹Σ) and Nb⁺(⁵D) + COS(¹Σ) → NbO⁺(³Σ⁻) + CS(¹Σ) are found to proceed through a quintet–triplet surface and the crossing regions were approximately determined. All of the results have been compared with existing experimental and theoretical data.