Magnetic doping of the golden cage cluster M@Au-16(-) (M=Fe,Co,Ni)

Structural, electronic, and magnetic properties of the golden cage doped with a transition-metal atom, MAu16- (M=Fe,Co,Ni), are investigated using trapped ion electron diffraction, photoelectron spectroscopy, and density-functional theory. The best agreement to experiment is obtained for endohedral M@Au-16(-) structures but with considerable distortions to the parent Au-16(-) cage. Fe@Au-16(-) and Co@Au-16(-) are found to have similar structures with C-2 symmetry while a C-1 structure is obtained for Ni@Au-16(-). The 4s electrons are observed to transfer to the Au-16 cage, whereas atomiclike magnetism due to the unpaired 3d electrons is retained for all the doped clusters.