In this work, we resolved the excited-state dynamics of the firstdiscovered photosensitiser, [Fe(bmip) 2 ] 2+ , using full-dimensional TSH dynamics simulations. In agreement with the recent XES experiment of Kunnus et al. , we observe branching of the excitedstate population into 3 MLCT and 3 MC, on early sub-ps timescales. According to the branching, we identify two main relaxation pathways: i) 1 MLCT → 3 MLCT → 3 MC → 1 GS with a short-lived 3 MLCT component (∼200-300 fs), and ii) 1 MLCT → 3 MLCT with a long-lived 3 MLCT intermediate (∼10 ps or longer lived). Similarly to our recent work on the singlet-triplet-quintet dynamics of the [Fe(terpy) 2 ] 2 complex (terpy = 2,2':6',2"-terpyridine), we obtain convincing agreement with experimentally resolved dynamics, which justify the accuracy of the utilised B3LYP* DFT/TD-DFT framework for MLCT-MC energetics and dynamics. Moreover, the consistency achieved for the initial dynamics using LVC and unconstrained full ab initio PESs further validates our results.