Covalent Excited States of Polyenes C2nH2n+2 (n = 2−8) and Polyenyl Radicals C2n-1H2n+1 (n = 2−8): An
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- 作者：Junjing Gu ; Yonghui Lin ; Ben Ma ; Wei Wu ; Sason Shaik
- 刊名：Journal of Chemical Theory and Computation
- 出版年：2008
- 出版时间：December 9, 2008
- 年：2008
- 卷：4
- 期：12
- 页码：2101-2107
- 全文大小：179K
- 年卷期：v.4,no.12(December 9, 2008)
- ISSN：1549-9626
文摘
The ab initio valence bond (VB) methods, VBSCF and VBCI, are applied to the ground states and the covalent excited states of polyenes C2nH2n+2 (n = 2−8) and polyenyl radicals C2n-1H2n+1 (n = 2−8). The excitation energy gap was computed at the ab initio VB level, which is in good agreement with the semiempirical VB method, VBDFT(s), and the experimental values as well as with the molecular orbital theory based methods, CASPT3 and MRCI. The ab initio VB wave functions of systems are also in very good agreement with those of the VBDFT(s) method, even though the former is based on the ab initio VB scheme while the latter is a semiempirical Hckel type method, in which no orbital optimization procedure is performed. The computational results show that the ab initio VB method is capable now of providing numerical accuracy not only for bond forming and breaking processes, as shown in the past, but also for excitation energies, as shown here. In addition, the computational results validate the efficiency of the VBDFT(s) method, which is a simple VB model with less computational effort but which provides intuitive insights into the excited states of conjugated molecules.