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气相中Zr活化CH_4分子C—H键的理论研究

A theoretical study of the mechanism of C—H bonding activation between Zr and CH_4
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摘要 采用密度泛函理论和高级电子相关耦合簇方法,在CCSD/6-311++G(3df,3pd)//B3LYP/6-311++G(3df,3pd)理论水平下,研究了两个自旋态下的Zr原子活化CH4分子中C—H键逐个夺取H原子的微观反应机理.通过计算,讨论了势能面交叉和可能的自旋翻转过程.用Harvey等的方法优化出最低能量交叉点(MECP),并计算了MECP处相应的自旋-轨道耦合常数(SOC),进一步讨论了Zr与CH4的反应中不同势能面之间的"系间窜越"(ISC)的可能性. The mechanism of the spin-forbidden reaction between Zr and CH4 on triplet and singlet potential energy surfaces（PESs） has been investigated at the CCSD/6-311＋＋G（3df,3pd）//B3LYP/6-311＋＋G（3df,3pd）levels.The minimum energy crossing points（MECPs）are obtained by the mathematical algorithm proposed of Harvey.The crossing points between the different potential energy surfaces and the possible spin inversion process are discussed by means of spin-orbit coupling（SOC） calculations.And further the possibility of the intersystem crossing is discussed.
作者 王永成 崔丹丹 耿志远 刘会文 王强
机构地区 西北师范大学化学化工学院
出处 《西北师范大学学报（自然科学版）》 CAS 北大核心 2010年第3期75-79,共5页 Journal of Northwest Normal University(Natural Science)
基金 甘肃省自然科学基金资助项目(0710RJZA115)
关键词 Zr活化CH4 密度泛函理论(DFT) 最低能量交叉点(MECP) 自旋-轨道耦合(SOC) Zr actives CH4 density functional theory（DFT） minimum energy crossing point（MECP） spin-orbit coupling（SOC）
分类号 O641.121 [理学—物理化学]
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参考文献18

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西北师范大学学报（自然科学版）
2010年 第3期

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