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Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface

[Image: see text] Dissociative chemisorption of O(2) on the Al(111) surface represents an extensively studied prototype for understanding the interaction between O(2) and metal surfaces. It is well known that the experimentally observed activation barrier for O(2) dissociation is not captured by con...

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Autores principales: Yin, Rongrong, Zhang, Yaolong, Libisch, Florian, Carter, Emily A., Guo, Hua, Jiang, Bin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6025882/
https://www.ncbi.nlm.nih.gov/pubmed/29843512
http://dx.doi.org/10.1021/acs.jpclett.8b01470
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author Yin, Rongrong
Zhang, Yaolong
Libisch, Florian
Carter, Emily A.
Guo, Hua
Jiang, Bin
author_facet Yin, Rongrong
Zhang, Yaolong
Libisch, Florian
Carter, Emily A.
Guo, Hua
Jiang, Bin
author_sort Yin, Rongrong
collection PubMed
description [Image: see text] Dissociative chemisorption of O(2) on the Al(111) surface represents an extensively studied prototype for understanding the interaction between O(2) and metal surfaces. It is well known that the experimentally observed activation barrier for O(2) dissociation is not captured by conventional density functional theory. The interpretation of this barrier as a result of spin transitions along the reaction path has been challenged by recent embedded correlated wave function (ECW) calculations that naturally yield an adiabatic barrier. However, the ECW calculations have been limited to a static analysis of the reaction pathways and have not yet been tested by dynamics simulations. We present a global six-dimensional potential energy surface (PES) for this system parametrized with ECW data points. This new PES provides a reasonable description of the site-specific and orientation-dependent activation barriers. Quasi-classical trajectory calculations on this PES semiquantitatively reproduce both the observed translational energy dependence of the sticking probability and steric effects with aligned O(2) molecules.
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spelling pubmed-60258822018-06-30 Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface Yin, Rongrong Zhang, Yaolong Libisch, Florian Carter, Emily A. Guo, Hua Jiang, Bin J Phys Chem Lett [Image: see text] Dissociative chemisorption of O(2) on the Al(111) surface represents an extensively studied prototype for understanding the interaction between O(2) and metal surfaces. It is well known that the experimentally observed activation barrier for O(2) dissociation is not captured by conventional density functional theory. The interpretation of this barrier as a result of spin transitions along the reaction path has been challenged by recent embedded correlated wave function (ECW) calculations that naturally yield an adiabatic barrier. However, the ECW calculations have been limited to a static analysis of the reaction pathways and have not yet been tested by dynamics simulations. We present a global six-dimensional potential energy surface (PES) for this system parametrized with ECW data points. This new PES provides a reasonable description of the site-specific and orientation-dependent activation barriers. Quasi-classical trajectory calculations on this PES semiquantitatively reproduce both the observed translational energy dependence of the sticking probability and steric effects with aligned O(2) molecules. American Chemical Society 2018-05-29 2018-06-21 /pmc/articles/PMC6025882/ /pubmed/29843512 http://dx.doi.org/10.1021/acs.jpclett.8b01470 Text en Copyright © 2018 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Yin, Rongrong
Zhang, Yaolong
Libisch, Florian
Carter, Emily A.
Guo, Hua
Jiang, Bin
Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title_full Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title_fullStr Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title_full_unstemmed Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title_short Dissociative Chemisorption of O(2) on Al(111): Dynamics on a Correlated Wave-Function-Based Potential Energy Surface
title_sort dissociative chemisorption of o(2) on al(111): dynamics on a correlated wave-function-based potential energy surface
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6025882/
https://www.ncbi.nlm.nih.gov/pubmed/29843512
http://dx.doi.org/10.1021/acs.jpclett.8b01470
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