Nanoclusters and nanoalloys of group 13 elements (B, Al, and Ga): benchmarking of methods and analysis of their structures and energies

Abstract

We investigated the structural and energetic properties of nanoclusters and nanoalloys composed of group 13 elements (B, Al, and Ga) up to a cluster size of 12. We conducted a comprehensive benchmark analysis of density functional and post-Hartree–Fock methods to identify efficient and accurate approaches for studying these systems using our benchmark dataset (BAlGa16) consisting of sixteen dimers and trimers. We compared different density functionals and post-Hartree–Fock methods using bond length and binding energy as parameters. B2PLYP closely follows CCSD(T) for geometry optimization, while REVPBE, BPBE, and PBE show cost-accuracy balanced performances. MRACPF was used as the reference for benchmarking energies, with NEVPT2 being the most accurate method, followed by CCSD(T) and DLPNO-CCSD(T). M06 and range-separated hybrid functionals perform well. Based on a cost-accuracy analysis, we recommend M06/def2-SVP as the preferred method. Additionally, we explored the structural evolution of pure, binary, and ternary clusters of group 13 elements up to 12 atoms, uncovering global and local minima. Ga clusters exhibited more rectangular faces compared to the predominantly trigonal faces of B and Al clusters. Binary clusters showed B in center positions, while Ga preferred outer positions, confirming the higher cohesion of B. The most favorable size of binary clusters (12) exhibited similar compositions of Al and Ga atoms. Compositions with 16.67–40% B, 16.67–60% Al, and 20–50% Ga were estimated to have negative mixing energies, indicating their relative stability.