Optical absorption of (Ag-Au)133(SCH3)52 bimetallic monolayer-protected clusters

The evolution of the optical absorption spectrum of bimetallic Ag-Au monolayer-protected clusters (MPC) obtained by progressively doping Ag into the experimentally known structure of Au-133(SR)(52) was predicted via rigorous time-dependent density-functional theory (TDDFT) calculations. In addition to monometallic Au-133(SR)(52) and Ag-133(SR)(52) species, 5 different (Ag-Au)(133)(SR)(52) homotops were considered with varying Ag content and site positioning, and their electronic structure and optical response were analyzed in terms of Projected Density Of States (PDOS), the induced or transition electron density, and Transition Component Maps (TCM) at selected excitation energies. It was found that Ag doping led to the effects rather different from those encountered in bare metal clusters. And it was also observed that Ag doping could produce structured spectral features, especially in the 3-4 eV range but also in the optical region if Ag atoms were located in the sub-staple region, as rationalized by the accompanying electronic analysis. Additionally, Au doping into the staples of Ag-rich MPC also gave rise to a more homogeneous induced electron density. These findings show the great sensitivity of the electronic response of MPC nanoalloy systems to the exact location of the alloying sites.