期刊
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
卷 205, 期 2-3, 页码 104-108出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jphotochem.2009.04.014
关键词
Aminoazobenzene; Isomerization mechanism; Potential energy surface; Ab initio
资金
- Key Project of Chinese Ministry of Education [209080]
The isomerization mechanism of the ground-state and the first single excited-state (S-0 and S-1) for 4-aminoazobenzene (4-AAB) was studied on the basis of the DFT-B3LYP and CASSCF calculations. The results indicate that the thermal cis-trans (E <-> Z) isomerization of 4-AAB mainly concerns the inversion mechanism, while the photoisomerization on the S-1 state involves the rotational pathway that is characterized by the S-1/S-0 conical intersection with a twisting structure. By means of the investigation on the geometrical parameters, it was found that the relaxation modes, which determine the decay dynamics of the excited states, are different for the E- and Z-isomers upon excited in the S-1 state. Moreover, the S-1 potential energy surface of 4-AAB is found to be similar to that of parent azobenzene. During the decay process of excited E-isomer through the rotation of the NN bond, however, the activation energy barrier of 4-AAB is lower than that of azobenzene, which suggests that the corresponding decay lifetime of S-1 excited E-4-AAB is smaller than that of E-azobenzene. (C) 2009 Elsevier B.V. All rights reserved.
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