Electron correlation effects in boron clusters B Qn (for Q = −1, 0, 1 and n ≤ 13) based on quantum Monte Carlo simulations

Abstract

We present all-electron quantum Monte Carlo simulations on the anionic, neutral, and cationic boron clusters B^Q_n with up to 13 atoms (Q = −1, 0, +1 and n ≤ 13). Accurate total energies of these clusters are obtained and an excellent agreement is reached with available experimental results for adiabatic and vertical detachment energies. We also perform very accurate Hartree–Fock calculations in the complete-basis-set limit where electron correlation is absent. In combination with the FN-DMC and HF-CBS results, we quantify the correlation effects and present the first attempt for a systematic investigation on the electron correlation effects in boron clusters. The obtained results show that, in general, electron correlation may contribute significantly to both the atomic and electronic structures of the boron clusters, manifested in the quantities such as the average binding energies of the clusters, atomic dissociation energies, detachment energies, and ionization potentials. For instance, the calculations indicate that the electron correlation maintains the bound state of cationic cluster B₂⁺ and it also contributes 99% of the detachment energy of the anionic cluster B₅⁻.