Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite.

Autor: Zhao Z; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany., Wang Y; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA., Yang X; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany., Quan J; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany., Krüger BC; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany., Stoicescu P; Georg-August-Universität Göttingen, Institut für physikalische Chemie, Göttingen, Germany., Nieman R; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA., Auerbach DJ; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany., Wodtke AM; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany.; Georg-August-Universität Göttingen, Institut für physikalische Chemie, Göttingen, Germany.; International Center for Advanced Studies of Energy Conversion, University of Goettingen, Göttingen, Germany., Guo H; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA. hguo@unm.edu., Park GB; Max-Planck-Institut für Multidisziplinäre Naturwissenschaften, Göttingen, Germany. barratt.park@ttu.edu.; Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, USA. barratt.park@ttu.edu.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2023 Jul; Vol. 15 (7), pp. 1006-1011. Date of Electronic Publication: 2023 May 22.
DOI: 10.1038/s41557-023-01204-2
Abstrakt: The formation of two-electron chemical bonds requires the alignment of spins. Hence, it is well established for gas-phase reactions that changing a molecule's electronic spin state can dramatically alter its reactivity. For reactions occurring at surfaces, which are of great interest during, among other processes, heterogeneous catalysis, there is an absence of definitive state-to-state experiments capable of observing spin conservation and therefore the role of electronic spin in surface chemistry remains controversial. Here we use an incoming/outgoing correlation ion imaging technique to perform scattering experiments for O( 3 P) and O( 1 D) atoms colliding with a graphite surface, in which the initial spin-state distribution is controlled and the final spin states determined. We demonstrate that O( 1 D) is more reactive with graphite than O( 3 P). We also identify electronically nonadiabatic pathways whereby incident O( 1 D) is quenched to O( 3 P), which departs from the surface. With the help of molecular dynamics simulations carried out on high-dimensional machine-learning-assisted first-principles potential energy surfaces, we obtain a mechanistic understanding for this system: spin-forbidden transitions do occur, but with low probabilities.
(© 2023. The Author(s).)
Databáze: MEDLINE
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