来自S的气体cis-stilbene的超快环闭反应
Shutaro Karashima1, Xincheng Miao2, Akio Kanayama1
1Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan.
气态cis-stilbene (cis-St) 发生超快环闭反应,形成二二二 (DHP). 这项研究显示,在分离的cis-St中,环闭优于 cis-trans异构.
科学领域:
- 摄影化学
- 分子动力学
- 超快速光谱
背景情况:
- cis-Stilbene (cis-St) 是 cis-trans 光异构化的基准.
- 在溶液中,cis-St形成低量子产量 (<0.19) 的二二.
- 在气态cis-St中环闭仍然未被确定,模拟预测低DHP量子产量 (0.04).
研究的目的:
- 识别和描述气态cis-stilbene的环闭反应.
- 在隔离条件下研究光刺激的cis-stilbene的动态.
- 为了确定气态cis-stilbene的反应产品的分支比.
主要方法:
- 使用极紫外线时间分辨率光电子光谱 (TRPES).
- 在SA3-XMS-CASPT2 ((2,2) 理论水平上进行了表面跳跃轨迹计算.
- 计算方法用于复制实验光谱和预测产品产量.
主要成果:
- 这是首次发现气态cis- stilbene的超快环闭反应.
- 计算机模拟成功复制了实验时间解析的光电子光谱.
- 预测的cis-stilbene:dihydrophenanthrene:trans-stilbene的分支比为0.55:0.41:0.04. 在该研究中,基因分支比为0.55:0.41:0.04.
结论:
- 光激发的气态cis-stilbene主要经历环闭,形成DHP.
- 对于分离的cis-stilbene而言,环闭是优于 cis-trans 异构化.
- 这项研究修改了先前对cis- stilbene的DHP形成的估计.
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