Intersystem crossing in the exit channel

Li, Hongwei; Kamasah, Alexander; Matsika, Spiridoula; Suits, Arthur G.

doi:10.1038/s41557-018-0186-5

Title: Intersystem crossing in the exit channel

Journal Article · 09 December 2018 · Nature Chemistry

DOI: https://doi.org/10.1038/s41557-018-0186-5 · OSTI ID:1595258

^[1]; Kamasah, Alexander ^[2]; Matsika, Spiridoula ^[3]; Suits, Arthur G. ^[2]

Univ. of Missouri, Columbia, MO (United States); U. Missouri
Univ. of Missouri, Columbia, MO (United States)
Temple Univ., Philadelphia, PA (United States)

We report that intersystem crossing (ISC), 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 ISC mechanism in the bimolecular reaction of O(³P) 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. Multireference ab initio calculations suggest, instead, that ISC 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. Finally, ISC then leads to a deep hydroxylamine well before OH elimination.

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Research Organization:: Univ. of Missouri, Columbia, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; ARO; National Science Foundation (NSF)

Grant/Contract Number:: SC0017130

OSTI ID:: 1595258

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 2 Vol. 11; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (6)

First-principles dynamics of collisional intersystem crossing: resonance enhanced quenching of C( ¹ D) by N ₂ An, Feng; Han, Shanyu; Hu, Xixi Physical Chemistry Chemical Physics, Vol. 21, Issue 17 https://doi.org/10.1039/c8cp07171c	journal	January 2019
A ConFlat iris diaphragm device for direct beam control and alignment inside a vacuum chamber Zhang, Yi C.; Lee, David Y. AIP Advances, Vol. 9, Issue 7 https://doi.org/10.1063/1.5095525	journal	July 2019
Spin-orbit coupling and vibronic transitions of two Ce(C ₄ H ₆ ) isomers probed by mass-analyzed threshold ionization and relativistic quantum computation Zhang, Yuchen; Cao, Wenjin; Yang, Dong-Sheng The Journal of Chemical Physics, Vol. 151, Issue 12 https://doi.org/10.1063/1.5123729	journal	September 2019
An unexpected spin flip alters the course of a chemical reaction Miller, Johanna L. Physics Today, Vol. 72, Issue 2 https://doi.org/10.1063/pt.3.4127	journal	February 2019
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Spin-Orbit Interactions in Ultrafast Molecular Processes Talotta, Francesco; Morisset, Sabine; Rougeau, Nathalie Physical Review Letters, Vol. 124, Issue 3 https://doi.org/10.1103/physrevlett.124.033001	journal	January 2020

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