Tuning the electronic properties of the golden buckyball by endohedral doping: M@Au₁₆⁻ (M=Ag,Zn, In)

Authors

Lei-Ming Wang, Washington State University, Richland
Rhitankar Pal, University of Nebraska-Lincoln
Wei Huang, Washington State University, Richland
Xiao Cheng Zeng, University of Nebraska-LincolnFollow
Lai-Sheng Wang, Washington State University, Richland, Washington

Date of this Version

2009

Comments

Published in THE JOURNAL OF CHEMICAL PHYSICS 130, 051101 (2009). Copyright © 2009 American Institute of Physics. Used by permission.

Abstract

The golden Au₁₆^- cage is doped systematically with an external atom of different valence electrons: Ag, Zn, and In. The electronic and structural properties of the doped clusters, MAu₁₆^- (M =Ag,Zn, In), are investigated by photoelectron spectroscopy and theoretical calculations. It is observed that the characteristic spectral features of ₁₆^-, reflecting its near tetrahedral (T_d) symmetry, are retained in the photoelectron spectra of MAu₁₆^-, suggesting endohedral structures with little distortion from the parent Au₁₆^- cage for the doped clusters. Density functional calculations show that the endohedral structures of MAu₁₆^- with T_d symmetry are low-lying structures, which give simulated photoelectron spectra in good agreement with the experiment. It is found that the dopant atom does not significantly perturb the electronic and atomic structures of Au₁₆^-, but simply donate its valence electrons to the parent Au₁₆^- cage, resulting in a closed-shell 18-electron system for Ag@ Au₁₆^-, a 19-electron system for Zn@ Au₁₆^- with a large energy gap, and a 20-electron system for In@ Au₁₆^-. The current work shows that the electronic properties of the golden buckyball can be systematically tuned through doping.