Published Research - Department of Chemistry


Date of this Version



THE JOURNAL OF CHEMICAL PHYSICS 134, (2011), pp. 054306. doi:10.1063/1.3533443


Copyright © 2011 American Institute of Physics. Used by permission.


The structural and electronic effects of isoelectronic substitution by Ag and Cu atoms on gold cluster anions in the size range between 13 and 15 atoms are studied using a combination of photoelectron spectroscopy and first-principles density functional calculations. The most stable structures of the doped clusters are compared with those of the undoped Au clusters in the same size range. The joint experimental and theoretical study reveals a new C3v symmetric isomer for Au13 , which is present in the experiment, but has hitherto not been recognized. The global minima of Au14 and Au15 are resolved on the basis of comparison between experiment and newly computed photoelectron spectra that include spin-orbit effects. The coexistence of two isomers for Au15 is firmly established with convincing experimental evidence and theoretical calculations. The overall effect of the isoelectronic substitution is minor on the structures relative to those of the undoped clusters, except that the dopant atoms tend to lower the symmetries of the doped clusters.