| DOI | Resolve DOI: https://doi.org/10.1063/1.475936 |
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| Author | Search for: Bérces, A.; Search for: Hackett, P. A.; Search for: Lian, Li; Search for: Mitchell, S. A.; Search for: Rayner, D. M. |
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| Format | Text, Article |
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| Subject | cluster reactivity; niobium; density functional theory; charge transfer; cluster formation reactions |
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| Abstract | Absolute 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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| Publication date | 1998-04-01 |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| NPARC number | 21277562 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | cdcdba68-9361-4a32-9b9c-47684347c0dd |
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| Record created | 2016-04-19 |
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| Record modified | 2020-03-20 |
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