收稿日期: 2010-07-15
修回日期: 2010-09-13
网络出版日期: 2011-07-15
基金资助
Supported by National Natural Science Foundation of China (20773161)
Theoretical study on CN-loss photodissociation of the C6H5CN+ ion in the low-lying electronic states
Received date: 2010-07-15
Revised date: 2010-09-13
Online published: 2011-07-15
Supported by
Supported by National Natural Science Foundation of China (20773161)
使用完全活化空间自洽场(CASSCF)和多组态的二级微扰理论(CASPT2)方法,对C6H5CN+离子去CN的光解离反应进行了研究.计算了12B1, 12A2, 12B2, 22B1 和 12A1电子态的去CN解离势能曲线.通过对渐近产物的能量、构型、电荷和自旋密度布居的分析,得出结论:12A1, 12B1, 12A2, 22B1 和 12B2的解离产物分别为C6H+5 (X1A1) + CN (X2Σ+)(第1解离限),C6H+5 (13B1) + CN (X2Σ+)(第2解离限),C6H+5 (11A2) + CN (X2Σ+)(第3解离限),C6H+5 (11B1) + CN (X2Σ+)(第4解离限)和 C6H+5 (X1A1) + CN (12Π)(第5解离限).
董华 , 陈波珍 , 于淑媛 . C6H5CN+离子不同电子态的去CN光解离的理论研究[J]. 中国科学院大学学报, 2011 , 28(4) : 448 -456 . DOI: 10.7523/j.issn.2095-6134.2011.4.004
CN-loss photodissociation of the C6H5CN+ ion has been studied within the C 2v symmetry using CASSCF and CASPT2 methods. The CASPT2//CASSCF dissociation potential energy curves (PECs) for the five lowest-lying states were calculated. By checking the relative energies, the fragmental geometries, and the charge and spin density populations of the asymptote products along the PECs, we conclude that the 12A1, 12B1, 12A2, 22B1, and 12B2 states of C6H5CN+ correlate with C6H+5 (X1A1) + CN (X2Σ+), C6H+5 (13B1) + CN (X2Σ+), C6H+5 (11A2) + CN (X2Σ+), C6H+5 (11B1) + CN (X2Σ+), and C6H+5 (X1A1) + CN (12Π), which are the first, second, third, fourth, and fifth dissociation limits, respectively.
Key words： C6H5CN+ ion; CASPT2; photodissociation
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