| 气相中W~+活化CO_2分解的自旋禁阻反应机理 |
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| 引用本文： | 刘玲玲,王永成. 气相中W~+活化CO_2分解的自旋禁阻反应机理[J]. 物理化学学报, 2010, 26(2) |
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| 作者姓名： | 刘玲玲 王永成 |
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| 作者单位： | 1. 兰州城市学院化学与环境科学学院,兰州,730070
2. 西北师范大学化学化工学院,兰州,730070 |
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| 基金项目： | The project was supported by the National Natural Science Foundation of China (20873102). 国家自然科学基金 |
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| 摘 要： | 用密度泛函理论中的UB3LYP方法,对W采用相对论校正赝势基组(SDD),对C、O采用6-311+G(3d)基组,研究了气相中不同自旋态W+活化CO2分解的反应机理.计算结果表明,W+活化CO2分解反应以六重态进入反应通道,经过六重态势能面到四重态势能面的系间窜越(ISC),最后产物WO+和CO以四重态离开反应通道.运用Harvey方法优化出最低能量交叉点(MECP),并计算了MECP处的自旋-轨道耦合(SOC)常数(494.95cm-1),势能面的交叉和在MECP处较强的自旋-轨道耦合作用降低了自旋禁阻反应能垒,为反应提供了一条低能反应路径,反应总放热量为122.33kJ.mol-1.
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| 关 键 词： | 密度泛函理论 W~+舌化 自旋禁阻反应 最低能量交叉点 自旋-轨道耦合 |
Spin-Forbidden Reaction Mechanism of CO_2 Cleavage Activated by W~+ in Gas Phase |
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| LIU Ling-Ling,WANG Yong-Cheng. Spin-Forbidden Reaction Mechanism of CO_2 Cleavage Activated by W~+ in Gas Phase[J]. Acta Physico-Chimica Sinica, 2010, 26(2) |
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| Authors: | LIU Ling-Ling WANG Yong-Cheng |
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| Affiliation: | LIU Ling-Ling1 WANG Yong-Cheng2,(1College of Chemistry , Environment Science,Lanzhou City University,Lanzhou 730070,P. R. China,2College of Chemistry , Chemical Engineering,Northwest Normal University,P. R. China) |
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| Abstract: | We investigated the spin-forbidden reaction mechanism of CO2 cleavage,activated by W+ in gas phase,using density functional theory (DFT,UB3LYP) with the relativistic effective core potential (ECP) of basis sets (SDD) for W and the 6-311+G(3d) basis set for C and O. The calculation results show that W+ initially closes to CO2 on the sextet surface,then the products,WO+ and CO,exit the channel on the quartet surface. The process involves an intersystem crossing (ISC) from the sextet to the quartet state. We o... |
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| Keywords: | Density functional theory W~+ activation Spin-forbidden reaction Minimum energy crossing point Spin-orbital coupling |
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