四氯化苯醌-二苯撑体系的光诱导电子转移研究

化学学报 ›› 2004, Vol. 62 ›› Issue (23): 2319-2322. 上一篇下一篇

研究论文

四氯化苯醌-二苯撑体系的光诱导电子转移研究

李柳鸣¹, 李泽荣¹, 段晓惠², 李象远²

1. 四川大学化学学院, 成都, 610065;
2. 四川大学化工学院, 成都, 610065

投稿日期:2004-02-03 修回日期:2004-07-06 发布日期:2014-02-17
通讯作者: 李象远,E-mail:xyli@scu.edu.cn E-mail:xyli@scu.edu.cn
基金资助:
教育部重点科技(No.02054)资助项目.

Theoretical Investigation on Photoinduced Electron Transfer between Chloranil and Biphenylene

LI Liu-Ming¹, LI Ze-Rong¹, DUAN Xiao-Hui², LI Xiang-Yuan²

1. College of Chemistry, Sichuan University, Chengdu 610065;
2. College of Chemical Engineering, Sichuan University, Chengdu 610065

Received:2004-02-03 Revised:2004-07-06 Published:2014-02-17

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摘要/Abstract

用从头算方法对四氯化苯醌-二苯撑体系分子间相互作用进行了理论计算研究.用MP2/6-31G^**方法,分别优化电子给体二苯撑,受体四氯化苯醌的稳定构型,用同样的方法优化配合物的层间距得到其最稳定构型,并计算了BSSE校正后的电子给受体配合物的稳定化能.用CIS/6-31++G^**方法,计算了给体、受体及配合物的电子激发态.理论计算验证了给体和受体间能形成稳定的电子给受体配合物,该配合物受光激发能直接产生电荷转移态.在球孔穴近似和点偶极近似下,对电荷转移吸收的理论计算结果进行了非平衡溶剂化能校正.经非平衡溶剂化能校正的电荷转移跃迁能与实验值符合较好.

关键词: 从头算方法, 光诱导电子转移, 电荷转移态, 光谱移动

Theoretical calculation has been performed for the photoinduced electron transfer between chloranil and biphenylene.The center-center distance between the donor and acceptor of the complex has been optimized by using MP2 method, and the counterpoise method has been adopted to consider the basis set superposition error.Four lowlying excited singlet states of chloranil-biphenylene (CL-BP) complex have been investigated by using the method of configuration interaction singles.It is concluded that CL and BP can form a stable electron donor-acceptor complex and light absorption can directly produce excited charge transfer state.Based on the approximation of spherical cavity and point dipole, the solvation correction of the absorption spectrum has been made for the charge transfer transition.The red shift of 0.443 eV was predicted.The result shows that the theoretical calculation agrees well with the experimental observations.

Key words: ab initio, photoinduced electron transfer, charge transfer state, spectral shift

引用此文

李柳鸣, 李泽荣, 段晓惠, 李象远. 四氯化苯醌-二苯撑体系的光诱导电子转移研究[J]. 化学学报, 2004, 62(23): 2319-2322.

LI Liu-Ming, LI Ze-Rong, DUAN Xiao-Hui, LI Xiang-Yuan. Theoretical Investigation on Photoinduced Electron Transfer between Chloranil and Biphenylene[J]. Acta Chimica Sinica, 2004, 62(23): 2319-2322.

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四氯化苯醌-二苯撑体系的光诱导电子转移研究

Theoretical Investigation on Photoinduced Electron Transfer between Chloranil and Biphenylene

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