AgPd, AuPd, and AuPt Nanoalloys with Ag- or Au-Rich Compositions: Modeling Chemical Ordering and Optical Properties

[Image: see text] Bimetallic nanoparticles have a myriad of technological applications, but investigations of their chemical and physical properties are precluded due to their structural complexity. Here, the chemical ordering and optical properties of AgPd, AuPd, and AuPt nanoparticles have been studied computationally. One of the main aims was to clarify whether layered ordered phases similar to L1(1) one observed in the core of AgPt nanoparticles [ J. Pirart; Nat. Commun.2019, 10, 198231040272] are also stabilized in other nanoalloys of coinage metals with platinum-group metals, or the remarkable ordering is a peculiarity only of AgPt nanoparticles. Furthermore, the effects of different chemical orderings and compositions of the nanoalloys on their optical properties have been explored. Particles with a truncated octahedral geometry containing 201 and 405 atoms have been modeled. For each particle, the studied stoichiometries of the Ag- or Au-rich compositions, ca. 4:1 for 201-atomic particles and ca. 3:1 for 405-atomic particles, corresponded to the layered structures L1(1) and L1(0) inside the monatomic coinage-metal skins. Density functional theory (DFT) calculations combined with a recently developed topological (TOP) approach [ S. M. Kozlov; Chem. Sci.2015, 6, 3868−388029218158] have been performed to study the chemical ordering of the particles, whose optical properties have been investigated using the time-dependent DFT method. The obtained results revealed that the remarkable ordering L1(1) of inner atoms can be noticeably favored only in small AgPt particles and much less in AgPd ones, whereas this L1(1) ordering in analogous Au-containing nanoalloys is significantly less stable compared to other calculated lowest-energy orderings. Optical properties were found to be more dependent on the composition (concentration of two metals) than on the chemical ordering. Both Pt and Pd elements promote the quenching of the plasmon.