| 气相VO（∑＋）与CH3OH（1^A′）分子自旋禁阻反应C—H，O—H键活化机理的理论研究 |
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| 引用本文： | 吉大方,王永成,耿志远,拉毛吉,马伟鹏. 气相VO（∑＋）与CH3OH（1^A′）分子自旋禁阻反应C—H，O—H键活化机理的理论研究[J]. 中国科学:化学, 2012, 0(6): 815-821 |
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| 作者姓名： | 吉大方 王永成 耿志远 拉毛吉 马伟鹏 |
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| 作者单位： | 西北师范人学化学化工学院,兰州730070 |
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| 摘 要： | 采用密度泛函理论（DFT）B3LYP与cCsD方法研究了二重态和四重态势能面自旋禁阻反应VO（∑’）活化cH30H（1^A′）分子c—H，0—H键的微观机理．通过自旋一轨道耦合的计算讨论了势能面交叉点和可能的自旋翻转过程．在MEcP处，四重态和二重态问的旋轨耦合常数为131．14cm^-1．自旋多重度发生改变，从四重态系间穿越到二重态势能面形成中间体2^IM1，导致反应势能面的势垒明显降低．
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| 关 键 词： | 密度泛函（DFT） 最低能量交叉点（MECP ） 自旋-轨道耦合（SOC） |
Theoretical study of the mechanism for C-H, O-H bond activation in spin-forbidden reaction between VO and CH30H in the gas phase |
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| JI DaFang,WANG YongCheng,GENG ZhiYuan,LA MaoJi,MA WeiPeng. Theoretical study of the mechanism for C-H, O-H bond activation in spin-forbidden reaction between VO and CH30H in the gas phase[J]. Scientia Sinica Chimica, 2012, 0(6): 815-821 |
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| Authors: | JI DaFang WANG YongCheng GENG ZhiYuan LA MaoJi MA WeiPeng |
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| Affiliation: | (College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China ＊Corresponding author (email： ycwang@163.com; wangyc@nwnu.edu.cn) |
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| Abstract: | The mechanism of the spin-forbidden reaction VO （Σ＋） ＋ CH3OH （JA′） on quartet and doublet potential energy surfaces （PESs） has been investigated by DFT of B3LYP and CCSD. Crossing points between the different potential energy surfaces and the possible spin inversion process are discussed by spin-orbit coupling （SOC） calculations. The values of the SOC constants at MECP are 131.14 cm^-1 between quartet and doublet PESs. The intersystem crossing （ISC） between different quartet and which obviously reduce energy barriers. doublet PESs would occur and has been produced 2^IM1, |
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| Keywords: | density functional theory （DFT） minimum energy crossing point （MECP） spin-orbit coupling （SOC） |
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