完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.author | Xu, Chao | en_US |
dc.contributor.author | Yu, Le | en_US |
dc.contributor.author | Gu, Feng Long | en_US |
dc.contributor.author | Zhu, Chaoyuan | en_US |
dc.date.accessioned | 2019-04-02T06:00:32Z | - |
dc.date.available | 2019-04-02T06:00:32Z | - |
dc.date.issued | 2018-10-07 | en_US |
dc.identifier.issn | 1463-9076 | en_US |
dc.identifier.uri | http://dx.doi.org/10.1039/c8cp02767f | en_US |
dc.identifier.uri | http://hdl.handle.net/11536/148263 | - |
dc.description.abstract | Global nonadiabatic switching on-the-fly trajectory surface hopping simulations at the 5SA-CASSCF(6,6)/6-31G quantum level have been employed to probe the photoisomerization mechanism of trans-azobenzene upon pi pi* excitation within four coupled singlet low-lying electronic states (S-0, S-1, S-2, and S-3). We have performed 586 sampling trajectories (331 starting from S-2 and 255 from S-3), and we found about half of the sampling trajectories staying on S-1 or S-2 states as resonances and the other half of them ending on the ground S-0 state as active trajectories. The present simulation has demonstrated that there are six distinct photoisomerization pathways which can be summarized as three categories; one is the newly opened inversion-inversion nonreactive isomerization pathway accounting for 40% (34%) of active trajectories at a time constant of 80 fs (320 fs), the other is the inversion-torsion reactive and nonreactive isomerization pathways accounting for 40% (20%) of active trajectories at a time constant of 880 fs (1700 fs), and the third is the torsion-torsion reactive and nonreactive isomerization pathways accounting for 20% (46%) of active trajectories at a time constant of 780 fs (1000 fs) upon S-2 (S-3) pi pi* excitation. The simulated total reactive quantum yield for trans-azobenzene photoisomerization upon S-2 (S-3) pi pi* excitation is about 0.11 (0.13) which is in good agreement with recent experimental results of 0.09-0.20. Furthermore, the newly opened inversion-inversion nonreactive isomerization pathway from the present simulation agrees well with cascade experimental measurements of the S-n -> S-1 -> S-0 relaxation mechanism in both branching ratio and time constant. | en_US |
dc.language.iso | en_US | en_US |
dc.title | Probing the pi -> pi* photoisomerization mechanism of trans-azobenzene by multi-state ab initio on-the-fly trajectory dynamics simulations | en_US |
dc.type | Article | en_US |
dc.identifier.doi | 10.1039/c8cp02767f | en_US |
dc.identifier.journal | PHYSICAL CHEMISTRY CHEMICAL PHYSICS | en_US |
dc.citation.volume | 20 | en_US |
dc.citation.spage | 23885 | en_US |
dc.citation.epage | 23897 | en_US |
dc.contributor.department | 交大名義發表 | zh_TW |
dc.contributor.department | 應用化學系 | zh_TW |
dc.contributor.department | 應用化學系分子科學碩博班 | zh_TW |
dc.contributor.department | National Chiao Tung University | en_US |
dc.contributor.department | Department of Applied Chemistry | en_US |
dc.contributor.department | Institute of Molecular science | en_US |
dc.identifier.wosnumber | WOS:000446766300068 | en_US |
dc.citation.woscount | 2 | en_US |
顯示於類別: | 期刊論文 |