Document Type


Journal/Book Title

Physical Chemistry Chemical Physics

Publication Date



Royal Society of Chemistry





First Page


Last Page



The most stable geometries of the coinagemetal (or regium) atom (Cu, Ag, Au) clusters Mn for n up to 6 are all planar, and adopt the lowest possible spin multiplicity. Clusters with even numbers of M atoms are thus singlets, while those with odd n are open-shell doublets. Examination of the molecular electrostatic potential (MEP) of each cluster provides strong indications of the most likely site of attack by an approaching nucleophile, generally one of two positions. A nucleophile (NH3 or HCN) most favorably approaches one particular M atom of each cluster, rather than a bond midpoint or face. In the closed-shell clusters, the interaction energies are highly dependent upon the intensity of the MEP, but this correlation fades for the open-shell systems studied in this work. The strength of the interaction is also closely related to the basicity of the nucleophile. Regium bond energies can be more than 30 kcal/mol and tend to follow the Au > Cu > Ag order. These interaction energies are in large part derived from Coulombic attraction, with a smaller orbital interaction contribution.

Included in

Chemistry Commons



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.