the ground-state equilibrium (Fig. ). Especially panel b shows that hydrogens (light red) are closer to the bipyridyl than oxygens (darker red), indicating that the ligand serves as hydrogen bond acceptor in the 3 MLCT state. This is consistent with the partial charges of the 3 MLCT diabatic states, shown in Section S2.4 in Figure , where notably the para-carbon atom of the bipyridyl ligand changes from positively to negatively charged from the ground state to the 3 MLCT states. Fig. -c also shows that the solvation shell decreases more at the axial cyanide ligands than at the equatorial ones. This can be traced to the fact that the lowest MLCT states involve the out-of-plane t 2g orbitals that are delocalized over the axial cyanides. For the 3 MC state (panel d-f), no significant changes in the bipyridyl solvent shell with respect to the ground state can be observed, as the MC excitation does not affect the ligand. Instead, a significant rearrangement of the cyanide solvation shell can be observed. Here, the strongest effect is the receding of the solvation shell from the equatorial cyanides, which correlates with the Fe-C bond length changes of the 3 MC states (Fig. ) and the corresponding RDF (Fig. ), i.e., the solvent is pushed outwards by the elongating Fe-C bonds.