Figure shows the excited-stated dynamics of [Fe(bmip) 2 ] 2+ , photoexcited to the lowest bright MLCT states, simulated by the RPBE, OPBE, and BLYP GGA functionals in comparison to our previous B3LYP* results (taken from ref. 28). As is clear from the figure, all three GGA-LVC methods yield rather similar results but different from B3LYP*-LVC. Although we observe a 3 MLCT/ 3 MC branching, it becomes rather weak as the 3 MC component becomes almost negligible, and no 3 MC decay and 1 GS population growth is seen; furthermore, a small but non-negligible fraction of excited-state population is stuck in the 1 MLCT states. Overall, the B3LYP* results are more consistent with the time-resolved experiment, taken as the reference, which is clearly indicative of a 3 MLCT/ 3 MC branching and 3 MC decay, already on sub-ps timescales. We now analyze the results of our dynamics simulations in terms of the LVC potentials along the Fe-ligand breathing mode (which is known to be the dominant mode for MLCT-MC dynamics ) shown in Figure . We find that the energetic separation of 3 MLCT-3 MC potentials practically vanishes in the GGA cases, while for B3LYP*, the separation of the minima is larger than 0.5 eV with the 3 MC being lower. We identify this modulation of 3 MLCT-3 MC energetics as the main factor responsible for the drastic decrease in the weight of the 3 MC component, observed for the GGA methods (see Figures ). We attribute the energy modulation to the inclusion of exact (Hartree-Fock) exchange in the hybrid B3LYP*, which affects both MLCT and MC states but with opposite signs; therefore, the separation of these state changes significantly. The quintet 5 MC state was experimentally found not to contribute to the excitedstate dynamics of [Fe(bmip) 2 ] 2+ ; we have thus not included it in the simulations. Nevertheless, we display its LVC PES in Figure (red curves) in order to assess qualitatively its potential impact on the dynamics. For the three GGA methods (Figures ), the 5 MC potential is significantly displaced from the region at which the dynamics predominantly occur, i.e., around the 3 MLCT/ 3 MC minima and the 3 MLCT/ 3 MC the crossings; therefore, the 5 MC states can here be safely neglected. In the case of B3LYP* (Figure ), the 5 MC states are still not expected to affect the 3 MLCT/ 3 MC branching, however, they might slightly alter the 3 MC decay, as the crossing with the lower 3 MC PESs becomes more accessible than for the GGAs. Still, the B3LYP* excited-state description is the one that is more consistent with the time-resolved experiments, as it reproduces the 3 MLCT/ 3 MC branching, which is the most striking feature of the dynamics of [Fe(bmip) 2 ] 2+ .