完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.author | Xu, Chao | en_US |
dc.contributor.author | Gu, Feng Long | en_US |
dc.contributor.author | Zhu, Chaoyuan | en_US |
dc.date.accessioned | 2019-04-02T06:00:45Z | - |
dc.date.available | 2019-04-02T06:00:45Z | - |
dc.date.issued | 2018-09-21 | en_US |
dc.identifier.issn | 1463-9076 | en_US |
dc.identifier.uri | http://dx.doi.org/10.1039/c8cp04164d | en_US |
dc.identifier.uri | http://hdl.handle.net/11536/148187 | - |
dc.description.abstract | A global switching on-the-fly trajectory surface hopping dynamics simulation at the 3SA-CASSCF(12,11)/6-31G* quantum level has been employed to probe the photo-induced Wolff rearrangement (WR) reaction of 5-diazo Meldrum's acid (DMA) within three low-lying electronic excited states. The present simulation predicted that the branching ratios for relaxing back to the ground state, isomerizing to diazirine, and reaction to ketene I via carbene I are 69% +/- 0.1, 3% +/- 0.4, and 28% +/- 0.1, which are in excellent agreement with those obtained by the femtosecond spectroscopy experiment, 67%, 3% and 30%, respectively. In particular, the present simulation revealed that the major WR reaction to ketene I pathway is stepwise via the excited-state to carbene I (17.8% +/- 0.2) and via the ground-state to carbene I (8.7% +/- 0.2), and the minor pathway is concerted synchronous (1.5% +/- 0.6). The photo-induced WR reaction of DMA has been quantitatively interpreted in terms of the distribution of extended seam surfaces as a function of CN dissociation bonds for two important conical intersections within three low-lying electronic excited states. Ultrafast dynamic time constants have been estimated to be about 500 fs +/- 120 fs and 180 fs +/- 80 fs for the stepwise and the concerted WR reaction to ketene I which are also in good agreement with those determined by the experiment. Therefore, the photo-induced excited-state WR reaction mechanism has been quantitatively revealed by the present real-time dynamics simulation. | en_US |
dc.language.iso | en_US | en_US |
dc.title | An excited-state Wolff rearrangement reaction of 5-diazo Meldrum's acid: an ab initio on-the-fly nonadiabatic dynamics simulation | en_US |
dc.type | Article | en_US |
dc.identifier.doi | 10.1039/c8cp04164d | en_US |
dc.identifier.journal | PHYSICAL CHEMISTRY CHEMICAL PHYSICS | en_US |
dc.citation.volume | 20 | en_US |
dc.citation.spage | 22681 | en_US |
dc.citation.epage | 22688 | 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:000445220500027 | en_US |
dc.citation.woscount | 0 | en_US |
顯示於類別: | 期刊論文 |