. radicals has to be described. For simulations of F 1s RIXS, we have used TD-DFT/CAM-B3LYP and DFT-ROCIS/B3LYP com-putations as implemented in ORCA to compute a one dimensional cut in the PES of relevant electronic states along a rigid scans of dissociation of a single S-F bond, see FIG. -S14 for DFT-ROCIS PES and FIG. -S21 for TD-DFT PES. The dissociation limit is not possible to account for in DFT, and TD-DFT used here only accounts for one-electron excitations(CIS). Hence, we only follow the scan to the point where the ground state wave function is predominantly single reference, i.e. a S-F distance of 1.31 Å to 2.16 Å as cross checked by a CASSCF(2,2) computation. This protocol yields the energies and the wave function for ground, valence-excited and core-excited states, i.e. |0 , |f and |i . The RIXS module is used to obtain the transition dipole moments, µ 0i (R) and µ if (R) for each |0 → |i and |i → |f transition, along the scan.