According to the two set of experiments, i.e., TOAS /XES , we simulate the photoexcitation of [Fe(bmip) 2 ] 2+ at 485/400 nm; this is illustrated in Figure , in which we display the ground and excited-state diabatic PESs along the breathing mode ν 14 26 , known to be the dominant mode for dynamics involving MC states . Our excited-state model includes 11 MLCT, 3 1 MC, 12 MLCT, and 6 3 MC states (we here note that the PESs and electronic couplings can vary for different components of a given manifold such as 1 MLCT, etc.) The excitation process is simulated by projection of the ground-state nuclear (Wigner) distribution to the excitedstate PES using a 0.1 eV energy window centered at the 2.55/3.10 eV (485/400 nm) excitation energies (see ESI, section S1, for further details). As seen in Figure , the two excitation schemes lead to different initial 1 MLCT states, with the lower one matching the initial 1 MLCT state of our previous QD simulations . Figure shows the simulated electronic population dynamics for the lower-energy 485 nm (Figure ) and higher-energy 400 nm (Figure ) excitation. We note that we base all further analysis on the diabatic electronic representation, as it is suited for discussion of MLCT-MC dynamics, i.e., it maintains the electronic character at any nuclear geometry. It is clear from Figure that the pump energy does not have any considerable effect on the simulated dynamics. In both cases, i.e., 485/400 nm, the initial excited state has dominant MLCT character, which is in line with the matching excitation energies and considerable oscillator strengths calculated at the Franck-Condon (FC) equilibrium geometry (see ESI, Table ); excitation into 1 MC states only appears as a minor component. The 1 MLCT population almost promptly, in ∼50 fs decays to MLCT via singlet-triplet ISC. We find that the 3 MLCT population consists of two branches: a component converted into MC in ∼200-300 fs, which then decays on a ps timescale, repopulating the ground state ( 1 GS), and a second one with a 3 MLCT population stable up to 4 ps. We recall that in our previous QD simula-tions , we did observe the latter long-lived (∼few ps) MLCT component, but not the former sub-ps 3 MLCT → 3 MC pathway. Note that in principle, the 3 MC states could also be populated directly from the 1 MLCTs 20 , however, we find that this direct channel is negligible (due to its very low occurrence), as revealed by the inspection of individual trajectories (see ESI, section S3); this analysis also confirms that the ground state is dominantly repopulated from the 3 MC states (90%) with a minor 3 MLCT → 1 GS component (10%). Importantly, our simulated population dynamics are in excellent agreement with the XES experiment of Kunnus et al. with the only discrepancy being in the branching ratio, as we identify the 3 MC component as the one with larger weight, whereas in the XES experiment it is 3 MLCT. However, the observed early sub-ps 3 MC component is missing in the assignment of the TOAS experiment of Liu et. al. , as well as in our previous QD studies .