Quantum chemistry calculations of the growth patterns, simulated photoelectron spectra, and electronic properties of LaASil (A = Sc, Y, La; l ≤ 10) compounds and their anions

Abstract

The growth patterns, simulated photoelectron spectra, and electronic properties of LaASi_l (A = Sc, Y, and La; l ≤ 10) compounds and their anions were studied via quantum chemistry calculations using the Perdew–Burke–Ernzerhof (PBE) method and unprejudiced structural searching software ABCluster. The results revealed that the growth patterns of the most stable structures of neutral and anionic LaASi_l showed an adsorptive mode. The lowest-energy structures (LESs) of the LaASi_l (l ≤ 7) clusters were similar, except for those of anionic LaYSi₄⁻ and LaYSi₅⁻ and neutral LaScSi₇. Additionally, we investigated and calculated the photoelectron spectra, vertical detachment energies, adiabatic electron affinities, relative stability, charge transfer, magnetic moment, and chemical bond analysis of the LaASi_l ground-state structures. The La₂Si_l clusters exhibited higher stability than the LaYSi_l and LaScSi_l systems owing to their higher dissociation energies (DEs). The DEs of the LESs in the LaASi₃ molecule are higher than those of other clusters. Thus, the LaASi₃ cluster shows potential as a building framework for Si-based cluster materials with good stability. The natural population analysis data and chemical bond analysis results showed that the spd hybridization of the orbitals of the metal atoms in the LaASi_l system occurred. Except for the LaScSi₉ and LaScSi₁₀ clusters, the neutral LaASi_l compounds transform into the corresponding anions when an extra electron is accepted by the Si clusters.