Finally, we analysed coherent oscillations along the Fe-N/Fe-C bonds in the 3 MC states. We emphasise that these oscillations can only be observed, i.e., vibrational coherence is preserved, if the 3 MC population rises fast enough with respect to the period of the oscillations (∼300 fs). As both the more recent XES/XSS data by Kunnus et al. and the TOAS data from the original work on [Fe(bmip) 2 ] 2+ by Liu et al. contain the same oscillatory compo-nent, appearing already at early times, this means that the 3 MC states had to be populated already at early sub-ps timescales; this thus clarifies the branching mechanism. We attribute the lack of the early 3 MC component in the TOAS assignment to the low sensitivity of TOAS to the electronic character. Our simulated coherent oscillations are in good agreement with those extracted from the time-resolved experiments, even if the damping (decoherence) is underestimated. We showed that the coherent oscillations with a period of ∼300 fs stem mostly from nuclear dynamics of the Fe-C bonds, which underlines the effect of covalency that has been identified as a key factor in the sensitivity of core-to-core XES to structural dynamics .