TY - JOUR
T1 - Photoisomerization mechanisms from trans, trans-1,4-diphenyl-1,3-butadiene
T2 - CASSCF on-the-fly trajectory surface hopping dynamic simulations
AU - Zheng, Xiaolei
AU - Zhai, Gaohong
AU - Gao, Wanqing
AU - Lei, Yibo
AU - Yu, Le
AU - Zhu, ChaoYuan
PY - 2016/4/7
Y1 - 2016/4/7
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84962010147&partnerID=8YFLogxK
U2 - 10.1039/c6cp00514d
DO - 10.1039/c6cp00514d
M3 - Article
AN - SCOPUS:84962010147
VL - 18
SP - 8971
EP - 8979
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 13
ER -