The above analysis clearly demonstrates that in contrast to the general discussion scheme of excited-state transition metal complexes, the 3 MLCT PESs of [Fe(bmip) 2 ] 2+ are displaced from the ground-state potential along several modes. All of these modes |) for all normal modes. For each mode, the 3 MLCT-3 MC component leading to the largest absolute difference is selected. Absolute differences above 0.02 eV originating from a significant κ 3 MLCT i > 0.02 eV value are highlighted in red. The numbers in eV next to mode labels are the largest 3 MLCT gradient components. b) 3 MLCT-3 MC coupling strengths (|λ possess dominant ligand character, which will be activated by electronic MLCT excitation. As seen above, several of these activated modes should be capable of facilitating the 3 MLCT → 3 MC conversion either by reducing the 3 MLCT-3 MC energy gap or by accounting for the 3 MLCT-3 MC coupling. Equipped with these insights, we now explicitly analyse the interplay of nuclear and 3 MLCT-3 MC electronic population dynamics. Figure shows the average trajectory along three out of the above identified ligand modes, as well as the 3 MC population, for the simulation with 400 nm excitation. The three modes, selected by the 3 MLCT and 3 MC nuclear gradients (see Figure ), are ν 55 and ν 91 , which are deformation modes of the middle pyridine rings with symmetric stretch-ing/compression of the Fe-N bonds, and ν 143 , a more complex mode involving deformation of all ligand rings as well as C-H wagging motion of the methyl groups. As seen in Figure , significant vibrational dynamics occur along all three modes during the initial 0-300 fs period, with the mean displacement along the selected modes continuously shifting towards a structure distorted from the initial equilibrium geometry ⟨q i ⟩ = 0. Crucially, these structural dynamics correlate excellently with the initial 3 MC population increase (Figure , black curve), signalling the role of excited-state ligand motion in the sub-ps 3 MLCT → 3 MC deactivation. We here recall that nuclear motion and electronic coupling can vary for different components of the 3 MLCT and 3 MC manifolds. Therefore, for certain components and initial conditions, no early 3 MLCT → 3 MC transition occurs (because, e.g., the 3 MLCT ligand motion is not strong enough to significantly decrease the 3 MLCT-3 MC energy gap), which is the reason for the branching observed in Figure (i.e., sub-ps 3 MLCT → 3 MC transition vs long-lived 3 MLCT).