Quantum chemical study of molecular properties of AsXn (X = F and Cl, n = 1–5) and AsXn− (X = F and Cl, n = 1–6)

Abstract

The molecular properties (i.e., molecular structures, vibrational frequencies, electron affinities, and bond dissociation energies) of AsXn (X = F and Cl, n = 1–5) and AsXn− (X = F and Cl, n = 1–6) were calculated using coupled-cluster singles and doubles with perturbative triples (CCSD(T)) with large basis sets up to quintuple-ζ level. The variations in the molecular structures were rationalized via molecular orbital analysis. The results of the calculations show that the electronic structures of AsCln (n = 1–5) and AsCln− (n = 1–6) are the same as those of AsFn (n = 1–5) and AsFn− (n = 1–6), respectively. The results of the CCSD(T) are generally in good agreement with the empirical data. Density functional theory methods were assessed to find the optimal functional, yielding results comparable to those obtained with CCSD(T). The recently developed functionals MN12-SX and MN15 showed good overall performance for calculating the molecular properties.