Systematic Investigation of the Structure, Stability, and Spin Magnetic Moment of CrM(n) Clusters (M = Cu, Ag, Au, and n = 2–20) by DFT Calculations

[Image: see text] Binary clusters of transition-metal and noble-metal elements have been gathering momentum for not only advanced fundamental understanding but also potential as elementary blocks of novel nanostructured materials. In this regard, the geometries, electronic structures, stability, and magnetic properties of Cr-doped Cu(n), Ag(n), and Au(n) clusters (n = 2–20) have been systematically studied by means of density functional theory calculations. It is found that the structural evolutions of CrCu(n) and CrAg(n) clusters are identical. The icosahedral CrCu(12) and CrAg(12) are crucial sizes for doped copper and silver species. Small CrAu(n) clusters prefer the planar geometries, while the larger ones appear as on the way to establish the tetrahedral CrAu(19). Our results show that while each noble atom contributes one s valence electron to the cluster shell, the number of chromium delocalized electrons is strongly size-dependent. The localization and delocalization behavior of 3d orbitals of the chromium decide how they participate in metallic bonding, stabilize the cluster, and give rise to and eventually quench the spin magnetic moment. Moreover, molecular orbital analysis in combination with a qualitative interpretation using the phenomenological shell model is applied to reveal the complex interplay between geometric structure, electronic structure, and magnetic moment of clusters. The finding results are expected to provide greater insight into how a host material electronic structure influences the geometry, stability, and formation of spin magnetic moments in doped systems.