| New ab initio Potential Energy Surfaces for Cl(2P3/2, 2P1/2)+H2 Reaction |
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| 作者姓名： | 蒋彬 谢代前 |
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| 作者单位： | 南京大学化学化工学院理论与计算化学研究所，教育部介观化学重点实验室，南京210093;南京大学化学化工学院理论与计算化学研究所，教育部介观化学重点实验室，南京210093 |
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| 摘 要： | 采用多参考组态相互作用的计算方法和很大的基组构造了Cl+H2反应体系的一组新的三维从头算势能面. 该势能面包含Cl+H2体系的能量最低的三个绝热态，并在非绝热近似下转化为四个非绝热势能面. 另外，旋轨耦合矩阵元也基于Breit-Pauli Hamil-tonian计算得到. 对角化这四个非绝热势能和两个旋轨耦合矩阵元组成的全耦合Hamiltonian，得到了三个考虑旋轨耦合后的绝热势能面.基于这组新势能面的非绝热动力学计算结果与最新的实验符合得很好，很好地解释了
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| 关 键 词： | 从头算势能面，非绝热，旋轨耦合，Cl(2P)+H2→HCl+H |
| 收稿时间： | 8/5/2009 12:00:00 AM |
New ab initio Potential Energy Surfaces for Cl(2P3/2, 2P1/2)+H2 Reaction |
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| Bin Jiang and Dai-qian Xie.New ab initio Potential Energy Surfaces for Cl(2P3/2, 2P1/2)+H2 Reaction[J].Chinese Journal of Chemical Physics,2009,22(6):601-604. |
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| Authors: | Bin Jiang and Dai-qian Xie |
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| Institution: | Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School
of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School
of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China |
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| Abstract: | New global three dimensional potential energy surfaces for the Cl+H2 reactive system have been constructed using accurate multireference configuration interaction calculations with a large basis set. The three lowest adiabatic potential energy surfaces correlating asymptotically with Cl(2P)+H2 have been transformed to a diabatic representation, which leads to a fourth coupling potential for non-linear geometries. In addition, the spin-orbit coupling surfaces have also been computed using the Breit-Pauli Hamiltonian. Properties of the new potential are described. Reaction dynamics based on the new potential agrees with the recent experimental results quite well. |
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| Keywords: | Potential energy surface Multi-reference configuration interaction Spin-orbit coupling Nonadiabatic effect |
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