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| CH3S与CH2SH自由基反应的密度泛函理论研究 | |
| 引用本文： | 刘艳,王艳丽,任宏江.CH3S与CH2SH自由基反应的密度泛函理论研究[J].计算机与应用化学,2012,29(4):479-482. |
| 作者姓名： | 刘艳 王艳丽 任宏江 |
| 作者单位： | 1. 西北工业大学理学院化学系,陕西,西安,710072;渭南师范学院化学化工系,陕西,渭南,714000 2. 西北工业大学理学院化学系,陕西,西安,710072 3. 西安文理学院化学系,陕西,西安,710065 |
| 基金项目： | 陕西省教育厅专项科研基金，渭南师范学院科研计划资助项目 |
| 摘 要： | 用量子化学从头算和密度泛函理论(DFT)对CH3S与CH2SH自由基反应进行了研究。在B3LYP/6-311+G(d,p)水平上优化了反应通道各驻点物种(反应物、中间体、过渡态和产物)的几何构型,用内禀反应坐标(IRC)计算和频率分析的方法对过渡态结构及连接性进行了验证。在QCISD(T)/6-311++G(d,p)水平上计算了各物种的单点能,并对总能量进行了零点能校正。研究结果表明,CH3S与CH2SH反应为多通道反应,有3条可能的反应通道。反应物首先通过C-S键相互作用形成链状碳-硫偶合中间体IM1,再经过裂解和脱氢气机理生成主要产物P1(CH3SH+CH2S)和次要产物P2和P3。根据势能面分析,所有反应均为吸热反应。相对于CH3S与CH2SH,各产物能量分别为(-175.2,335.5和331.5)kJ.mol-1。 |
| 关 键 词： | CH3S CH2SH 密度泛函理论 反应机理 |
Density functionary theory study on the radical reactions between CH3S and CH2SH |
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| Liu Yan , Wang Yanli , Ren Hongjiang.Density functionary theory study on the radical reactions between CH3S and CH2SH[J].Computers and Applied Chemistry,2012,29(4):479-482. | |
| Authors: | Liu Yan Wang Yanli Ren Hongjiang |
| Affiliation: | 1.Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education,School of Natural and Applied Sciences,Northwestern Polytechnical University,Xi’an,710072,Shaanxi,China)(2.Department of Chemistry and Chemical Engineering,Weinan Teachers University,Weinan,714000,Shaanxi,China)(3.Department of Chemistry,Xi’an University of Arts and Science,Xi’an,710065,Shaanxi,China) |
| Abstract: | A detailed theoretical survey of the potential energy surface(PES) for the reaction CH3S with CH2SH is carried out at the QCISD(t)/6-311++G(d,p)//B3LYP/6-311+G(d,p) level.The geometries,vibrational frequencies,and energies of all stationary points involved in the title reaction are calculated at the B3LYP/6-311+G(d,p) level.More accurate energy information is provided by single-point calculations at QCISD(t)/6-311++G(d,p) level.Relationships of reactants,intermediates,transition states and products are confirmed by the intrinsic reaction coordinate(IRC) calculations.The results show that the initial association of CH3S with CH2SH is found to be a barrierless process.Firstly it forms the energy-rich adducts IM1 through the C-S bond.Then,form the main product P1(CH3SH+CH2S) and the secondary products P2 and P3 via the different channels.The energies of products P1-P3 are(-175.2,335.5 and 331.5) kJ.mol-1 relative to those of reactants. |
| Keywords: | CH3S CH2SH density functionary theory reaction mechanism |
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