Prediction of Structures and Atomization Energies of Small Silver Clusters, (Ag) n , n < 100

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 117; no. 34; pp. 8298 - 8313
• Main Authors: Chen, Mingyang, Dyer, Jason E., Li, Keijing, Dixon, David A.
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 29.08.2013
• Subjects: Atomic and molecular clusters; Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Coupled cluster theory; Density-functional theory; Electronic structure of atoms, molecules and their ions: theory; Environmental Molecular Sciences Laboratory; Exact sciences and technology; Physics; Spectroscopy and geometrical structure of clusters; Studies of special atoms, molecules and their ions; clusters; Cluster size; Inorganic compounds; Ground states; Theoretical study; Metal clusters; Isomers; Bond lengths; Genetic algorithms; Geometrical structure; Silver; Electron correlations; Transition elements; Density functional method; Spin state; Coupled cluster method; Atomic clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/jp404493w

Neutral silver clusters, Ag n , were studied using density functional theory (DFT) followed by high level coupled cluster CCSD(T) calculations to determine the low energy isomers for each cluster size for small clusters. The normalized atomization energy, heats of formation, and average bond lengths were calculated for each of the different isomeric forms of the silver clusters. For n = 2–6, the preferred geometry is planar, and the larger n = 7–8 clusters prefer higher symmetry, three-dimensional geometries. The low spin state is predicted to be the ground state for every cluster size. A number of new low energy isomers for the heptamer and octamer were found. Additional larger Ag n structures, n < 100, were initially optimized using a tree growth-hybrid genetic algorithm with an embedded atom method (EAM) potential. For n ≤ 20, DFT was used to optimize the geometries. DFT with benchmarked functionals were used to predict that the normalized atomization energies (⟨AE⟩s) for Ag n start to converge slowly to the bulk at n = 55. The ⟨AE⟩ for Ag99 is predicted to be ∼50 kcal/mol.