DFT-Based Global Optimization of Sub-nanometer Ni–Pd Clusters

Abstract

The Mexican enhanced genetic algorithm has been used to study the structural and energetic properties of Pd, Ni, and Ni−Pd nanocluster structures with 3−10 atoms. Density functional theory (DFT) calculations have been performed to investigate the structural behavior, spin magnetic moment, and stability as a function of cluster size and composition. Various stability criteria (for example, binding energies, second differences in energy, and mixing/excess energies) have been used to evaluate the energetics, structure, and tendency to segregation in subnanometer Ni−Pd clusters. The ability of the approach in searching for global minima (i.e., the lowest-energy isomers) has been assessed using a systematic homotop search of monosubstituted clusters and the preferred doping sites.

Dressing of Cu Atom over Nickel Cluster Stimulating the Poisoning-Free CO Oxidation: An Ab Initio Study

“…To ensure the validity of the adopted computational method, the binding energy per atom and bond length of Ni 2 , NiCu, and Cu 2 systems were calculated using LDA and PBE functionals and presented in Table . The computed values obtained with PBE functional are in better agreement with experimental , and other theoretical data − compared to LDA functional. To determine the lowest-energy structures of Ni n +1 clusters (2 ≤ n ≤ 12), possible geometries were inspected and summarized in Figure S1 of the Supporting Information (SI) with their corresponding relative energy (Δ E ).…”

“…Our results on ECN and pointgroup symmetry (structure) of pure Ni clusters are fall in with the other reports. 46,48 Interestingly, for Ni 13 , icosahedral geometry is recognized as the lowest energy structure by LDA functional, while, the PBE functional shows preference for the hcp one. 48 As shown in Figures 1 and 3 3.1.2.…”

Magnetic moment quenching in small Pd clusters in solution

“…The D 2d bicapped octahedron shown in Fig. 2a is the previously reported global minimum for PBE [10,25,63,64]. It shows a 4 μ B ground state in our calculations.…”

Palladium clusters, free and supported on surfaces, and their applications in hydrogen storage

“…The structure of Pd n clusters has been investigated by geometry optimization using density functional theory (DFT) 23,24 and other methods. For clusters up to about Pd 20 , extensive searches have been performed by combining DFT with genetic algorithms, 25,26 basin hopping strategies, 27 particle swarm optimization, 28 or using a large set of initial structures. 22,29–31 Fig.…”

“…22,29–31 Fig. 1 shows the structures of Pd 3 to Pd 10 , taken from the work of Granja-DelRío et al , 25 who used a genetic algorithm and the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional. 32 The structures, symmetry point groups, binding energies (with respect to the separated free atoms), spin magnetic moments, and average Pd–Pd neighbour distances are given in Table 1.…”