標題: Photoisomerization mechanisms from trans, trans-1,4-diphenyl-1,3-butadiene: CASSCF on-the-fly trajectory surface hopping dynamic simulations
作者: Zheng, Xiaolei
Zhai, Gaohong
Gao, Wanqing
Lei, Yibo
Yu, Le
Zhu, Chaoyuan
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 7-Apr-2016
摘要: We have employed the SA2-CAS(4,4)/6-31G ab initio method together with an on-the-fly global-switching trajectory surface hopping algorithm to simulate photoisomerization reaction dynamics from reactant trans, trans-1,4-diphenyl-1,3-butadiene (DPB) to products cis,trans-DPB and cis,cis-DPB. This topic has been extensively studied experimentally and the present theoretical study is the first to simulate DPB photoisomerization reaction dynamics as far as we know. With total 600 sampling trajectories, 300 actively contribute to isomerization reaction via two conical intersections between the electronic ground and the first excited states. Simulated quantum yields of photoisomerization to cis, trans-DPB and cis, cis-DPB are 0.09 and 0.045, which are in good agreement with the experimental values of 0.07-0.25 and 0.02, respectively. The lifetime of the first excited state is estimated as 702 fs. The present simulation has shown two reactive photoisomerization mechanisms, namely one bond twist (OBT) and bicycle pedal (BP), and two non-reactive photoisomerization mechanisms, namely single bond torsion (SBT) and reverse torsion (RT) with respect to the central backbone CC bonds. We believe that the present theoretical work can benefit the experiments on photoisomerization of DPB derivates.
URI: http://dx.doi.org/10.1039/c6cp00514d
http://hdl.handle.net/11536/133421
ISSN: 1463-9076
DOI: 10.1039/c6cp00514d
期刊: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume: 18
Issue: 13
起始頁: 8971
結束頁: 8979
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