Superior performance of range-separated hybrid functionals for describing σ* ← σ UV-vis signatures of three-electron two-center anions.

We assess the efficiency of density functionals for the description of UV-vis signatures of temporary anions featuring a three-electron two-center bond, along a representative set of systems ranging from (pseudo)dihalides to disulfide radical anions (dimethyl disulfide and lipoate). While BH&HLYP and B3LYP have been predominantly applied to perform such simulations so far, we outline the significantly improved performance of several recently proposed functionals, including range-separated hybrids for the computation of these specific vertical transitions.