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Intersystem crossing in the exit channel.
Nature Chemistry 2018 December 11
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(3 P) 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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