To this end, the explicit atomic structures used for computing the S1-state torsion profile do not fully match those of the S0-state based scan, albeit featuring the same torsion angle θ. In fig. , the conical intersection is prepared by matching the MM-based S1 profile to the MM-based S0 torsion barrier. In TD-DFT, the conical intersection prevents numerical assessment of S1 energies for the HTI structures near θ = 90° as already demonstrated by Plötner and Dreuw. To assess the energy shift between T1 and S1, we instead used the S0-Z and S0-E configurations at 90°, which showed offsets of 2•ΔEexchange = 0.80 and 0.74 eV, respectively. Our excited-state MM models fitted to the T1-based DFT energies of the torsion profile, are thus suggested to use a constant shift of 0.77±0.03 eV to mimic the corresponding S1-states.