Ground state MD simulations reveal that a breaking of the D 3 symmetry due to torsion of the aryl rings occurs both in vacuum and in solvent environments. If the dihedral angles defining the orientation of the rings (see Table ) are not equal, the symmetry of the molecule is broken. As shown in Fig. , the degeneracy of the HOMO and HOMO-1 orbitals is preserved in the optimized geometry with equal dihedral angles (a), but is lifted in the geometry taken from an MD snapshot in methanol (b), with a corresponding lifting of the degeneracy of the S 1 and S 2 excitation energies. Furthermore, it is found that the amount of torsional motion of the aryl rings varies in different environments. The MD trajectory in vacuum shows almost identical average values of the three dihedral angles to those in the optimized vacuum structure, but with a large standard deviation indicating relatively unrestricted torsional motion of the rings (see Table ). This dihedral motion causes a 0.08 eV energy splitting in the broad S 1 and S 2 absorption bands computed along the vacuum trajectory using the cumulant approach (see SI Sec. 1). The large amount of spectral broadening observed in vacuum is a result of the unconstrained rotation of the aryl rings, resulting in the combined spectrum due to both S 1 and S 2 excitations only exhibiting a very minor peak splitting of 0.07 eV (see Fig. ). The average values of the aryl ring dihedral angles in solution, computed along the MD trajectories in methanol and toluene, show a larger deviation from the values of the optimized ground state geometry when compared with the vacuum trajectory, indicating that some amount of torsion and thus a broken symmetry of the molecule is permanently stabilized by the solvent environment. Specifically, the recorded mean dihedral angles for two aryl rings in toluene are found to differ by almost 6°, indicating a sustained symmetry-breaking of the chromophore structure along the MD trajectory (see Table ). This observation may be related to the bulkiness of the toluene molecule and π-stacking interactions with the aryl rings, which prevents free rotation observed in vacuum. Additionally, the standard deviations of the dihedral angles are found to be higher in vacuum than in toluene, further suggesting that the rotation of the aryl rings in toluene is significantly constrained by the condensed phase environment. In contrast, the inclusion of a Cl -counterion in the MD dynamics for both methanol and toluene condensed phase environments was found to have only a negligible effect on the computed mean and standard deviation of the dihedral angles of the aryl rings (see SI Sec. 1), as compared with trajectories generated by ignoring the presence of the counterion. However, from Fig. ) it is clear that a close association of CV with Cl -, as is observed in the optimized structure in vacuum, leads to a strong breaking of the molecular orbital degeneracy, with a corresponding S 1 -S 2 splitting that is significantly larger than for an MD snapshot taken from the trajectory in methanol (Fig. ).