Having described the vertical excitations and identifying ωPBEh as a method for providing the overall excited state characters effectively, we now turn to an analysis of the excited state minimum geometries in solution for Cz-BDT and Cz-AQ. First, the geometries of the S 0 , S 1 , and T 1 minima are optimised using ωPBEh/def2-SVP within toluene solvation, considering that toluene was used in the experimental studies considered. The S 1 is always optimised with TDDFT whereas, following Ref. 6, we investigate two possibilities for optimising the T 1 minimum, an excited-state optimisation using TDDFT and a formal groundstate optimisation using UKS. The key structural parameters are outlined in Table , and the geometries are shown in Fig. . Generally speaking, we find that upon excitation the molecules planarise, i.e. dihedral angles become smaller, and that the interring distances become shorter. Cz-BDT retains the two-fold symmetry in all computations whereas we observe symmetry-breaking in the excited state for Cz-AQ. Starting with Cz-BDT, we find that variations in the Cz-Ph torsion θ 1 /θ 1 are relatively minor whereas the θ 2 /θ 2 values become close to zero for S 1 and T 1 . This means that the Ph-BDT-Ph system becomes almost planar after photoexcitation, see also Figure , effectively producing one extended π-system, and we will revisit this point below. In Cz-Aq on the other hand, we find clear evidence of symmetry-breaking for the excited state minima: the angles on one side of the molecule (θ 1 and θ 2 ) remain at values close to the S 0 minimum, however θ 1 and θ 2 are reduced. The T 1 minimum for Cz-AQ, optimised with either TDDFT or UKS, has one of the Ph bridges almost in plane with the core, whilst for the S 1 minimum this lies at an intermediate value between the S 0 and T 1 minima. We proceed by discussing the excited states at the individual geometries. For this purpose, we consider two different approaches, the standard LR-PCM method also used for the TDDFT optimisations, as well as a more involved state-specific approach, which is expected to provide an improved description of CT states. For the vertical absorption (S 0 ), we use the perturbative (ptSS) approach whereas for emission (S 1 /T 1 ) we use the equilibrated SS-PCM approach. Starting the discussion with Cz-BDT, we present data for the lowest four triplet and three singlet excited states in Figure . In comparison to the unsolvated model in Fig , we find similar state characters when using the LR-PCM model at the S 0 geometry for Cz-BDT. However, we find that the ππ * states (blue, green, red) are somewhat shifted down in energy producing a different ordering of the states. This shift also removes the accidental degeneracy found between the bright ππ * state and the nπ * state that was seen in the unsolvated calculation. Calculating the same excitations under the ptSS solvation scheme gives stabilisation to states with charge transfer character, and we now find the bright CT-dominated S 2 state at 2.71 eV which is in nearperfect agreement with the experimental absorption maximum of 2.65 eV.