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Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite
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 o...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10322699/ https://www.ncbi.nlm.nih.gov/pubmed/37217785 http://dx.doi.org/10.1038/s41557-023-01204-2 |
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author | Zhao, Zibo Wang, Yingqi Yang, Ximei Quan, Jiamei Krüger, Bastian C. Stoicescu, Paula Nieman, Reed Auerbach, Daniel J. Wodtke, Alec M. Guo, Hua Park, G. Barratt |
author_facet | Zhao, Zibo Wang, Yingqi Yang, Ximei Quan, Jiamei Krüger, Bastian C. Stoicescu, Paula Nieman, Reed Auerbach, Daniel J. Wodtke, Alec M. Guo, Hua Park, G. Barratt |
author_sort | Zhao, Zibo |
collection | PubMed |
description | 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. [Image: see text] |
format | Online Article Text |
id | pubmed-10322699 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-103226992023-07-07 Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite Zhao, Zibo Wang, Yingqi Yang, Ximei Quan, Jiamei Krüger, Bastian C. Stoicescu, Paula Nieman, Reed Auerbach, Daniel J. Wodtke, Alec M. Guo, Hua Park, G. Barratt Nat Chem Article 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. [Image: see text] Nature Publishing Group UK 2023-05-22 2023 /pmc/articles/PMC10322699/ /pubmed/37217785 http://dx.doi.org/10.1038/s41557-023-01204-2 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Zhao, Zibo Wang, Yingqi Yang, Ximei Quan, Jiamei Krüger, Bastian C. Stoicescu, Paula Nieman, Reed Auerbach, Daniel J. Wodtke, Alec M. Guo, Hua Park, G. Barratt Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title | Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title_full | Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title_fullStr | Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title_full_unstemmed | Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title_short | Spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
title_sort | spin-dependent reactivity and spin-flipping dynamics in oxygen atom scattering from graphite |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10322699/ https://www.ncbi.nlm.nih.gov/pubmed/37217785 http://dx.doi.org/10.1038/s41557-023-01204-2 |
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