Fig. 2. Electronic states with possible involvement in the LMCT decay dynamics of Fe(CN)63–. (a) Electronic configurations of the proposed GS, LMCT and Quartet electronic states. The electrons excited with respect to the GS configuration are shown in orange. (b) One-dimensional projections of potential energy surfaces of the considered electronic states, along scans of octahedral symmetry with varied Fe–C distance and frozen C–N bonds. Vertical excitation with 400 nm optical pump from the GS to LMCT surface occurs close to an intersection between the LMCT and Quartet surfaces. (c) Optimized structures (as obtained in D2h symmetry) of the LMCT state (@LMCT) and Quartet state (@Quartet) compared to the shaded GS structure (@GS).
