Reactivity of niobium clusters with nitrogen and deuterium

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DOIResolve DOI: http://doi.org/10.1063/1.475936
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TypeArticle
Journal titleThe Journal of Chemical Physics
ISSN0021-9606
Volume108
Issue13
Pages54765490
Subjectcluster reactivity; niobium; density functional theory; charge transfer; cluster formation reactions
AbstractAbsolute rate coefficients are reported for reactions of Nbₙ clusters(n=2–20) with D₂ and N₂ at 280, 300, and 370 K. Most clusters are highly reactive but there are conspicuous exceptions at n=8, 10, and 16 for both D₂ and N₂. The origin of this trend in reactivity with cluster size and the reason why D₂ and N₂ show similar trends are discussed. Density functional theory(DFT)electronic structure calculations have been used to investigate the details of the reactions for the smallest clusters Nb₂ and Nb₈ with H₂ and N₂. The steric and electronic requirements for dissociation of H₂ and N₂ are described in terms of frontier orbital interactions. The main conclusion from the DFT calculations is that complete dissociation of H₂ or N₂ requires charge transfer by transit of an avoided crossing between neutral and ionic potentials. This idea is extended to larger clusters by using a simple charge transfer model that predicts an inverse correlation between reactivity and an appropriately defined effective ionization potential. Such a correlation is observed and indicates that the effective ionization potential is the dominant influence on reactivity.
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PublisherAIP Publishing
LanguageEnglish
Peer reviewedYes
NPARC number21277562
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Record identifiercdcdba68-9361-4a32-9b9c-47684347c0dd
Record created2016-04-19
Record modified2017-03-23
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