期刊
NATURE CHEMISTRY
卷 11, 期 2, 页码 123-128出版社
NATURE PORTFOLIO
DOI: 10.1038/s41557-018-0186-5
关键词
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资金
- Office of Science, Office of Basic Energy Science, Division of Chemical Science, Geoscience and Bioscience of the US Department of Energy [DE-SC0017130]
- ARO [W911NF-17-1-0099]
- NSF [CHE-1800171]
- U.S. Department of Energy (DOE) [DE-SC0017130] Funding Source: U.S. Department of Energy (DOE)
Intersystem crossing plays an important role in photochemistry. It is understood to be efficient when heavy atoms are present due to strong spin-orbit coupling, or when strongly bound long-lived complexes are formed that increase the chance of finding the singlet-triplet intersection seam. Here we present evidence for a different intersystem crossing mechanism in the bimolecular reaction of O(P-3) with alkylamines. In crossed-beam experiments, product velocity-flux maps are measured for aminoalkyl radicals produced from H abstraction from the methyl group, which also gives OH radicals as co-fragments. The low translational-energy release and isotropic angular distributions of the products indicate that such reactions undergo the formation of a complex before OH and aminoalkyl are produced. However, there is no well on the triplet potential energy surface that could support such a complex. Multi-reference ab initio calculations suggest, instead, that intersystem crossing occurs in the exit-channel region due to the long-range dipole-dipole interaction between the nascent radical product pair coupled with the vanishing singlet-triplet splitting at long range. Intersystem crossing then leads to a deep hydroxylamine well before OH elimination.
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