Thermally-induced chemical-order transitions in medium-large alloy nanoparticles predicted using a coarse-grained layer model

A new coarse-grained layer model (CGLM) for efficient computation of axially symmetric elemental equilibrium configurations in alloy nanoparticles (NPs) is introduced and applied to chemical-order transitions in Pt-Ir truncated octahedra (TOs) comprising up to tens of thousands of atoms. The model is based on adaptation of the free energy concentration expansion method (FCEM) using coordination-dependent bond-energy variations (CBEV) as input extracted from DFT-computed elemental bulk and surface energies. Thermally induced quite sharp transitions from low-T asymmetric quasi-Janus and quasi ball-and-cup configurations to symmetric multi-shells furnish unparalleled nanophase composite diagrams for 1289-, 2406- and 4033-atom NPs. At even higher temperatures entropic atomic mixing in the multi-shells gradually intensifies, as reflected in broad heat-capacity Schottky humps, which become sharper for much larger TOs (e.g., ∼10 nm, ∼30000 atoms), due to transformation to solid-solution-like cores.