Theoretical study on molecular properties of SbXn (X = F and Cl, n = 1–5) and SbXn− (X = F and Cl, n = 1–6) including spin–orbit coupling.

High‐level ab initio and density functional theory (DFT) calculations were performed to calculate the molecular properties of SbXn (X = F and Cl, n = 1–5) and SbXn− (X = F and Cl, n = 1–6), such as molecular structure, vibrational frequency, electron affinity (EA), and bond dissociation energy (BDE). The spin–orbit (SO) effect on the molecular properties was investigated using the SODFT method. The bond lengths optimized by the coupled‐cluster singles and doubles with perturbative triples method are in good agreement with the experimental values. The calculated vibrational frequencies agreed reasonably well with the available experimental values except for those of SbX4− (X = F and Cl) because the polar solvent affected the experimental results. SbX3 and SbX4− (X = F and Cl), whose Sb oxidation states are +3, exhibit substantial EAs and BDEs, respectively. The SO effect on SbX− and SbX2− (X = F and Cl) was considerable. [ABSTRACT FROM AUTHOR]