Ag6Cl4: the first silver chloride with rare Ag6 clusters from an ab initio study

Abstract

The first diamagnetic semiconducting silver subhalide, Ag₆Cl₄, featuring rare subvalent Ag₆ clusters with 2e⁻–6c bonds, 1D argentophilic d¹⁰–d¹⁰ intercluster interactions and 3D ionic connectivity ensured by Cl atoms has been predicted employing Density Functional Theory. Ag₆Cl₄ carries all unique features of Ag⁺ so far observed only in selected metal-rich oxides and as such represents an important addition to the discussion of the special bonding properties of silver with a filled d¹⁰-shell. Having appreciable formation enthalpy and dynamical stability, Ag₆Cl₄ should be in principle possible to synthesize as a metastable phase relative to AgCl.