Structure and bonding in polybromide anions Br−(Br2)n (n = 1-6)

► DFT calculations are performed on Br−(Br2)n (n = 1-6) complexes. ► For n = 1, the symmetric Br3- anion is the local minimum. ► For n = 2-6, Br2 molecules bind to the central Br− anion to form stable complexes. ► QTAIM analyses reveal the presence of closed-shell interactions.