Magnetic doping of a thiolated-gold superatom: First-principles density functional theory calculations

The Au25 (SR) 18 - cluster is a new member in the superatom family which features a centered icosahedral shell (Au13) protected by six RS (AuSR) 2 motifs (RS- being an alkylthiolate group). Here we show that this superatom can be magnetically doped by replacing the center Au atom with Cr, Mn, or Fe. We find that Cr- and Mn-doped clusters have an optimized magnetic moment of 5 Bohr magnetons while the Fe-doped cluster has an optimized magnetic moment of 3 Bohr magnetons. Although the dopant atom's local magnetic moment makes a major contribution to the total moment, the icosahedral Au12 shell is also found to be significantly magnetized. Our work here provides a scenario of magnetic doping of a metal-cluster superatom which is protected by ligands and made by wet chemistry.