Ultrafast Ring Closure Reaction of Gaseous <i>cis</i>-Stilbene from S<sub>1</sub>(ππ*)
Ultrafast Ring Closure Reaction of Gaseous <i>cis</i>-Stilbene from S<sub>1</sub>(ππ*)
复制标题
S<sub>1</sub>(ππ*) 气态<i>顺</i>-二苯乙烯的超快闭环反应
DOI：
10.1021/jacs.2c12266
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发表时间：
2023
影响因子：
15
通讯作者：
Suzuki Toshinori
中科院分区：
文献类型：
--
作者：
Karashima Shutaro;Miao Xincheng;Kanayama Akio;Yamamoto Yo-ichi;Nishitani Junichi;Kavka Nikita;Mitric Roland;Suzuki Toshinori
顺式二苯乙烯（cis-St）是一种已知的顺式-光转异构化的基准体系，在溶液中也产生量子产率小于0.19的4a，4 b-二氢菲（DHP）。然而，闭环反应，从来没有被确定为gaseouscis-St，最近的计算模拟预测的量子产率DHP仅为0.04。在本研究中，我们确定了一个超快环闭合反应的gaseouscis-St的第一次使用极紫外时间分辨光电子能谱。在SA 3-XMS-CASPT 2（2，2）理论水平上的表面跳跃轨迹计算再现了所观察到的时间分辨光电子能谱的特征，并预测cis-St：DHP：trans-St支化比为0.55：0.41：0.04，与以前的估计相反。结果表明，光激发的顺式苯乙烯有利于环关闭的顺式-反式异构体在孤立的条件下。
cis-Stilbene (cis-St) is a well-known benchmark system forcis–transphotoisomerization.cis-St also produces 4a,4b-dihydrophenanthrene (DHP) in solution with a quantum yield of less than 0.19. The ring closure reaction, however, has never been identified for gaseouscis-St, and a recent computational simulation predicted the quantum yield of DHP to be only 0.04. In the present study, we identified an ultrafast ring closure reaction of gaseouscis-St for the first time using extreme ultraviolet time-resolved photoelectron spectroscopy. Surface hopping trajectory calculations at the SA3-XMS-CASPT2(2,2) level of theory reproduce the features of the observed time-resolved photoelectron spectra and predict thecis-St:DHP:trans-St branching ratio to be 0.55:0.41:0.04, in contrast with previous estimates. The results indicate that photoexcitedcis-St favors ring closure overcis–transisomerization under the isolated condition.