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Ab Initio Molecular Dynamics Simulations of Nitrogen/VN(001) Surface Reactions: Vacancy-Catalyzed N-2 Dissociative Chemisorption, N Adatom Migration, and N-2 Desorption
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Physics. Linköping University, Faculty of Science & Engineering.
University of Illinois, IL 61801 USA.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-2837-3656
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, Faculty of Science & Engineering.
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2016 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 23, 12503-12516 p.Article in journal (Refereed) PublishedText
Abstract [en]

We use density-functional ab initio molecular dynamics to investigate the kinetics of N/VN(001) surface reactions at temperatures ranging from 1600 to 2300 K. N adatoms (N-ad) on VN(001) favor epitaxial atop-V positions and diffuse among them by transiting through 4-fold hollow (FFH) sites, at which they are surrounded by two V and two N surface atoms. After several atop-V -amp;gt; FFH -amp;gt; atop-V jumps, isolated N adatoms bond strongly with an underlying N surface (N-surf) atom. Frequent N-ad/N-surf pair exchange reactions lead to N-2 desorption, which results in the formation of an anion surface vacancy. N vacancies rapidly migrate via in-plane (110) jumps and act as efficient catalysts for the dissociative chemisorption of incident N-2 molecules. During exposure of VN(001) to incident atomic N gas atoms, N-ad/N-ad recombination and desorption is never observed, despite a continuously high N monomer surface coverage. Instead, N-2 desorption is always initiated by a N adatom removing a N surface atom or by energetic N gas atoms colliding with N-ad or N-surf atoms. Similarities and differences between: N/VN(001) vs. previous N/TiN(001) results, discussed on the basis of temperature-dependent ab initio electronic structures and chemical bonding, provide insights for controlling the reactivity of NaCl-structure transition-metal nitride (001) surfaces via electron-concentration tuning.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2016. Vol. 120, no 23, 12503-12516 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-130283DOI: 10.1021/acs.jpcc.6b02652ISI: 000378196200021OAI: oai:DiVA.org:liu-130283DiVA: diva2:950594
Note

Funding Agencies|Knut and Alice Wallenberg Foundation (Isotope Project) [2011.0094]; Swedish Research Council (VR) Linkoping Linnaeus Initiative LiLi-NFM [2008-6572, 2014-5790, 2013-4018]; Swedish Government Strategic Research Area Grant in Materials Science on Advanced Functional Materials (through Swedens innovation agency VINNOVA) [MatLiU 2009-00971]

Available from: 2016-08-01 Created: 2016-07-28 Last updated: 2016-09-07

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The full text will be freely available from 2017-05-19 12:01
Available from 2017-05-19 12:01

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Sangiovanni, DavideHultman, LarsChirita, ValeriuPetrov, IvanGreene, Joseph E
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