期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 118, 期 45, 页码 10433-10447出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp504174t
关键词
-
资金
- NSF [CHE-1057481]
- Ohio Supercomputer Center
- Department of Chemistry, University of Cincinnati
- Natural Sciences Research Council of Canada (NSERC)
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057481] Funding Source: National Science Foundation
The irradiation of trans-vinylketones 1a-c yields the corresponding cis isomers 2a-c. Laser flash photolysis of 1a and 1b with 308 and 355 nm lasers results in their triplet ketones (T-1K of 1), which rearrange to form triplet 1,2-biradicals 3a and 3b, respectively, whereas irradiation with a 266 nm laser produces their cis-isomers through singlet reactivity. Time-resolved IR spectroscopy of 1a with 266 nm irradiation confirmed that 2a is formed within the laser pulse. In comparison, laser flash photolysis of 1c with a 308 nm laser showed only the formation of 2c through singlet reactivity. At cryogenic temperatures, the irradiation of 1 also resulted in 2. DFT calculations were used to aid in the characterization of the excited states and biradicals involved in the cis-trans isomerization and to support the mechanism for the cis-trans isomerization on the triplet surface.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据