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

Abstract 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 Ag n Au 13− n ( n = 1, 2, 3, 5, 7, 8, 9, 12) and hollow Ag n Au 13− 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.