English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

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

MPS-Authors
/persons/resource/persons21506

Fielicke,  André
Molecular Physics, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21614

Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21859

Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Fielicke, A., Helden, G. v., Meijer, G., Pedersen, D. B., Simard, B., & Rayner, D. M. (2006). Size and charge effects on the binding of CO to late transition metal clusters. The Journal of Chemical Physics, 124, 194305-1-194305-8. doi:10.1063/1.2196887.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0011-04AD-3
Abstract
We report on the size and charge dependence of the C–O stretching frequency, ν(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (ConCO–/0/+), anionic, neutral, and cationic rhodium clusters (RhnCO–/0/+), and cationic nickel clusters (NinCO+) for n 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) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO 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 n increases. At large n, ν(CO) approaches asymptotes that are not the same as found for ν(CO) on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.