Charge transfer driven surface segregation of gold atoms in 13-atom Au–Ag nanoalloys and its relevance to their structural, optical and electronic properties

The structural, optical and electronic properties of 13-atom Ag-Au nanoalloys are determined by a combination of global optimization using semi-empirical potentials and density functional theory calculations. A family of Au surface-segregated structures are found for core-shell AgnAu13-n (n = 1, 2, 3, 5, 7, 8, 9,12) and hollow AgnAu13-n (n = 4, 6,10,11) clusters, whose stability is enhanced by directional charge transfer. The atomic ordering in core-shell structures is related to the electric dipole moment and odd-numbered surface Au-atom clusters have high moments. Their ferroelectric and ferromagnetic properties provide a potential approach for tailoring their surface plasmonic modes. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.