Reactivity of niobium clusters with nitrogen and deuterium
10.1063/1.475936
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
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.

Bibliography

Bérces, A., Hackett, P. A., Lian, L., Mitchell, S. A., & Rayner, D. M. (1998). Reactivity of niobium clusters with nitrogen and deuterium. The Journal of Chemical Physics, 108(13), 5476–5490.

Authors 5
  1. A. Bérces (first)
  2. P. A. Hackett (additional)
  3. Li Lian (additional)
  4. S. A. Mitchell (additional)
  5. D. M. Rayner (additional)
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Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 8:38 a.m.)
Deposited 2 years, 1 month ago (July 9, 2023, 3:32 p.m.)
Indexed 1 year, 6 months ago (Feb. 11, 2024, 5:57 a.m.)
Issued 27 years, 5 months ago (April 1, 1998)
Published 27 years, 5 months ago (April 1, 1998)
Published Print 27 years, 5 months ago (April 1, 1998)
Funders 0

None

@article{B_rces_1998, title={Reactivity of niobium clusters with nitrogen and deuterium}, volume={108}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.475936}, DOI={10.1063/1.475936}, number={13}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Bérces, A. and Hackett, P. A. and Lian, Li and Mitchell, S. A. and Rayner, D. M.}, year={1998}, month=apr, pages={5476–5490} }