Growth pattern and electronic and magnetic properties of Cr-doped silver clusters

Growth pattern and electronic and magnetic properties of AgnCr (n = 1-16) clusters have been investigated via density functional theory (DFT) combined with CALYPSO structure search method. The optimized geometry shows that the growth of the global minimum structures of AgnCr clusters have obvious rule. when n > 12, silver atoms grow around an icosahedron which is almost unchanged in each structure. Analyses of electronic properties indicate that the doped Cr atom can only enhance the stability of larger silver clusters. Optical absorption and photoelectron spectra of AgnCr isomers have been predicted and can be used for their structural identification. The icosahedral Ag12Cr cluster with large energy level gap can be seen as a superatom. The adsorption capacity of Cr atom in AgnCr cluster to CO is much higher than that of free Cr atom. The intensity of IR and Ramam spectra can be dramatically enhanced when CO is absorbed on AgnCr cluster that Cr atom is encapsulated by Ag atoms. Moreover, the red shift of IR and Raman spectra of CO adsorbed on these clusters is also very small compared to free CO. Magnetism calculations show that the magnetic moment of AgnCr clusters decreases linearly from n = 6 to 12 and increases linearly from n = 12 to 16. The total magnetic moment of AgnCr cluster is mainly localized on the Cr atom. The change of magnetic moment of Cr atom is related to the charge transfer between Cr and Ag atoms.