传能反应O(1D)+CO2(1∑g+)→O(3P)+CO2(1∑g+)中间物机理的理论研究

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (4): 689.

传能反应O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)中间物机理的理论研究

杨光辉¹, 张鑫¹, 孟庆田¹, 韩克利¹, 孙家锺²

1. 中国科学院大连化学物理研究所分子反应动力学国家重点实验室, 大连 116023;
2. 吉林大学理论化学研究所理论化学与计算国家重点实验室, 长春 130023

收稿日期:2003-05-06 出版日期:2004-04-24 发布日期:2004-04-24
通讯作者: 杨光辉(1964年出生),男,博士,教授,从事量子化学研究.E-mail:ghyang@dicp.ac.cn E-mail:ghyang@dicp.ac.cn
基金资助:
吉林大学理论化学与计算国家重点实验室开放项目基金资助

Theoretical Studies on the Intermediate Complex Mechanism ofthe Energy Transfer Reaction of O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)

YANG Guang-Hui¹, ZHANG Xin¹, MENG Qing-Tian¹, HAN Ke-Li¹, SUN Chia-Chong²

1. Center for Computational Chemistry, State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute ofChemical Physics, Chinese Academy of Sciences, Dalian 116023, China;
2. State Key Laboratory of theoretical andComputational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Received:2003-05-06 Online:2004-04-24 Published:2004-04-24

摘要/Abstract

摘要： 利用abinitio量子化学方法研究了自旋禁阻的传能反应O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)的反应机制,通过中间化合物CO₃的单、三重态的势能面交叉点的确认,证明了中间物传能机理的可行性.同时计算了交叉点处的自旋-轨道偶合和面间跃迁几率,进一步证明了中间化合物CO₃的形成在传能过程中的重要作用.

关键词: O(¹D)与CO₂(¹&sum, _g⁺)碰撞传能, 势能面交叉, 自旋-轨道偶合, 跃迁几率

Abstract: The reaction mechanism of spin-forbidden energy transfer reaction O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺) was investigated by ab initio quantum chemistry methods. The conical intersection of the two surfaces of CO₃ intermediate complex with multipl-spin electronic states was searched by using CASSCF(6,8) /6-311G^* method. The intermediate complex channel are supported by the calculations of spin-orbit coupling and transition probability.

Key words: Collision transfer energy of O(¹D) with CO₂, Portential energy surface crossing, Spin-orbital coupling, Transition probability

中图分类号:

O641

TrendMD:

杨光辉, 张鑫, 孟庆田, 韩克利, 孙家锺. 传能反应O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)中间物机理的理论研究. 高等学校化学学报, 2004, 25(4): 689.

YANG Guang-Hui, ZHANG Xin, MENG Qing-Tian, HAN Ke-Li, SUN Chia-Chong . Theoretical Studies on the Intermediate Complex Mechanism ofthe Energy Transfer Reaction of O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺). Chem. J. Chinese Universities, 2004, 25(4): 689.

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传能反应O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)中间物机理的理论研究

Theoretical Studies on the Intermediate Complex Mechanism ofthe Energy Transfer Reaction of O(¹D)+CO₂(¹∑_g⁺)→O(³P)+CO₂(¹∑_g⁺)

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