Figure shows the population dynamics of [Fe(terpy) 2 ] 2+ simulated by B3LYP, PBE0, and LC-BLYP. We here recall that, as noted in the Computational Methods section, we did not carry out TSH dynamics simulations on [Fe(terpy) 2 ] 2+ using CAM-B3LYP-LVC PESs due to the observed 3 MLCT/ 3 MC mixing at the ground-state geometry (which did not allow to match the DFT/TD-DFT and CASPT2 states). The population dynamics of [Fe(terpy) 2 ] 2+ simulated by the two global hybrids, B3LYP and PBE0, shown in Figure and 8b, are in good overall agreement with the B3LYP* results, as well as the timeresolved XES experiment. Namely, all these data are consistent with a 1,3 MLCT → 3 MC → 5 MC photorelaxation mechanism and the simulated timescales agree for B3LYP, B3LYP*, and PBE0. Furthermore, the non-exponential character of the 5 MC population rise is also reproduced by B3LYP and PBE0. However, the 5 MC-3 MC oscillations caused by coherent vibrational motion along the Fe-N breathing mode in the 5 MC states do not appear in our B3LYP and PBE0 results. One possible reason for the absence of the oscillations is the loss of vibrational coherence, i.e., the 5 MC populations rise occurs on a slower timescale as compared to the vibrational period of ∼300 fs; however this is clearly not the case as seen in Figures and. Another more likely explanation in the present case is that the trajectories while propagating in the 5 MC manifold do not reach the 5 MC/ 3 MC intersection, at which population transfer can occur. Analysis of the B3LYP and PBE0 PESs shown in Figures 9a and 9b and comparison to the B3LYP* ones (Figure ) support this interpretation as for B3LYP and PBE0, the 5 MC/ 3 MC crossing gets significantly displaced from the 5 MC minimum. Finally, we discuss the population dynamics of [Fe(terpy) 2 ] 2+ simulated by the range-separated LC-BLYP method. As seen in Figure , these results for [Fe(terpy) 2 ] 2+ are very different (even qualitatively) from those obtained by all other methods, as the 5 MC population decays on a sub-ps timescale and 3 MC emerges as the dominant excited-state manifold at 1 ps. This is clearly in contradiction with the experimental data evidencing that all excited-state population is converted into 5 MC on a sub-ps timescale; specifically the 3 MC population is depleted in ∼500 fs. We attribute the vanishing 5 MC population in the LC-BLYP simulation to the significantly increased energy of the 5 MC states relative to the 3 MCs. As seen in Figure , the 5 MC potentials calculated by LC-BLYP are shifted by 1.5 eV as compared to the 5 MC PESs calculated by B3LYP and PBE0, which places them above the 3 MC states; this explains the strikingly different population dynamics obtained by the LC-BLYP and B3LYP/PBE0 simulations.