Open AccessOxides of small Rhodium clusters: Theoretical investigation of experimental reactivities
Author(s) -
Dan J. Harding,
R. D. Davies,
Stuart R. Mackenzie,
Tiffany R. Walsh
Publication year - 2008
Publication title -
the journal of chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.071
H-Index - 357
eISSN - 1089-7690
pISSN - 0021-9606
DOI - 10.1063/1.2981810
Subject(s) - rhodium , chemistry , dissociation (chemistry) , density functional theory , cluster (spacecraft) , oxide , carbon monoxide , reactivity (psychology) , inorganic chemistry , trioxide , cationic polymerization , catalysis , computational chemistry , polymer chemistry , organic chemistry , medicine , sulfur , alternative medicine , pathology , computer science , programming language
Density functional theory is used to investigate the structures of cationic rhodium cluster oxides, Rh(6)O(m) (+) (m=1,4). On the monoxide and dioxide, the oxygen atoms occupy bridge sites, while on trioxide and tetroxide clusters, high-coordination sites are favored. A range of spin multiplicities are investigated for each cluster, with high spin multiplicities found to be less favored for the oxides compared with the naked metal clusters. The dissociation of nitric oxide on low-energy isomers of Rh(6)O(4) (+) is investigated and found to be unfavorable compared to molecular adsorption due to a combination of thermodynamic and kinetic factors. These calculations are consistent with, and help to account for, the experimentally observed reactivity of rhodium and rhodium oxide clusters with nitric oxide [M. S. Ford et al., Phys. Chem. Chem. Phys. 7, 975 (2005)]
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