Size and charge effects on the binding of CO to late transition metal clusters

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DOIResolve DOI: http://doi.org/10.1063/1.2196887
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TypeArticle
Journal titleThe Journal of Chemical Physics
Volume124
Issue19
Article number194305
Pages194305-1194305-8
Subjectatomic clusters; bonds (chemical); carbon compounds; cobalt; negative ions; nickel; positive ions; rhodium; vibrational states
AbstractWe report on the size and charge dependence of the C–O stretching frequency, ν(CO)ν(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (ConCO−∕0∕+)(ConCO−∕0∕+), anionic, neutral, and cationic rhodium clusters (RhnCO−∕0∕+)(RhnCO−∕0∕+), and cationic nickel clusters (NinCO+)(NinCO+) for nn up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to ν(CO)ν(CO) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO π∗π* orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as nn increases. At large nn, ν(CO)ν(CO) approaches asymptotes that are not the same as found for ν(CO)ν(CO) on the single crystalmetal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
NPARC number12327439
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Record identifier4a6088f0-ac3c-4a7d-96ab-f0c4cdb56121
Record created2009-09-10
Record modified2017-03-23
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