Metal–metal interactions in an open d-shell system with cuprite structure

Abstract

The formation of directional metal–metal interactions and multicenter bonds is for the first time revealed in a cuprite structure of Pd₂O with a partially open d shell employing Density Functional Theory with evolutionary algorithms for crystal structure prediction. Two Pd₂O forms, featuring arrays of parallel zigzag Pd chains and a 2D network of corner-shared Pd₄ clusters, respectively, with appreciable thermodynamic stability, are predicted to compete for the ground state structure. This study presents the first detailed description of Pd(I)–Pd(I) bonding in an inorganic compound.