Figure shows the LVC potentials of [Fe(bmip) 2 ] 2+ obtained by the global and range-separated hybrid DFT/TD-DFT methods, along the breathing normal mode. In general, the MC states are lowered with respect to the MLCTs when compared to the B3LYP* potentials shown in Figure . This is the reason for the two main features observed in the simulated dynamics, namely, the involvement of 1 MC as they get below the bright 1 MLCT at the ground-state equilibrium geometry and the short 3 MLCT lifetime. In addition, for B3LYP, PBE0 and CAM-B3LYP, the potential role of the 5 MC state increases as its PES is lowered and thus moves into the region which is mostly accessed during the dynamics; this can be illustrated by the location of the crossing between the 5 MC potential with those of the lowest 3 MLCT and 3 MC states, which is very close to the 3 MLCT and 3 MC minima. For LC-BLYP, however, the 5 MC curve is placed significantly higher; the 5 MC minimum actually is located higher than the minimum of the lowest 3 MC state, similarly to the GGA cases (see Figures ), for which the 5 MC state can safely be neglected. We attribute the drastic difference between the 5 MC curves calculated by the two range-separated hybrids CAM-B3LYP and LC-BLYP shown in Figures and to the fixed fraction of exact exchange that is 19% for CAM-B3LYP (very close to B3LYP with 20% exact exchange) but 0% for LC-BLYP. We therefore arrive to the conclusion regarding the 5 MC state that it would have a major effect on the dyanmics for B3LYP, PBE, and CAM-B3LYP, but not for LC-BLYP.