The symmetry breaking of CV and the resulting splitting of the S 1 and S 2 absorption band found in experiment thus arises from a combination of two main factors: the rotation of the aryl rings and the interaction with the condensed-phase environment (such as solvent and the Cl -counterion). To probe the effect of the solvent environment on the spectral lineshape, we compute cumulant spectra for MD trajectories for CV in methanol and toluene in the absence of a counterion. The results are displayed in Fig. , in comparison with the experimental CV spectra in toluene and methanol taken from Ref. 1 and 2, respectively. The calculated spectrum in methanol is found to be good agreement with the experimental spectrum in terms of the lineshape and peak positions, showing an S 1 -S 2 splitting that is larger than in vacuum (see Table ). The origins of this good agreement will be discussed in detail in Sec. III B. However, the same method, when applied to calculate the absorption spectrum in toluene, yields a poor agreement with experiment, as the splitting between the peaks is is severely underestimated compared to what is observed experimentally. Indeed, the observed S 1 -S 2 splitting is only slightly larger than that observed for CV in vacuum and smaller than in methanol, in contrast to the experimentally observed trend of increased splitting in nonpolar solvent. This apparent failure of the MD-based cumulant approach to qualitatively describe the absorption lineshape of CV in toluene will be investigated in section III C.