In this section we go beyond the bulk solvent description and isolate the effect of specific chromophore-solvent interactions. To further analyze how the solvent dynamics control the spectral broadening, we compute the spectral density and the corresponding linear absorption spectrum considering different specific solvent environments for the vertical excitation energies with the same QM/MM AIMD trajectory. To isolate the spectral contributions of only the chromophore, we compute the TDDFT vertical excitation energies with all solvent stripped away. To isolate the effect of the strong peripheral H-bonds formed from the CV + amine donor, we include only those four methanol solvent molecules in the MM region of our QM/MM vertical excitation energy calculations, see Figure . We also examine the effect of the solvent interacting with the π-system of the chromophore by including the four methanol solvent molecules closest to CV + within the cylindrical axial region, with one of those solvent molecules forming the axial H-bond with the CV + amine acting as an acceptor that we analyzed previously, see Figure . We also isolate the effect of the single H-bonding axial methanol molecule by including it in the excitation energy calculations as it goes from being 9.0 Å away from the chromophore during the start of the trajectory to being completely H-bonded to the chromophore at the end of the 60 ps. Lastly, we consider the effect of treating the surrounding nearby solvent at the QM level of theory instead of as fixed MM point charges. For the various specific chromophore-solvent interactions, the resulting spectral densities and linear absorption spectra are shown in Figure . The absorption spectra are once again aligned according to their maxima, with the corresponding unshifted spectra shown in the SI, section S8. In the spectral density in Figure , we see that the chromophore-only snapshots produce low intensity in the low-frequency region, as expected where there is no solvent contribution. The corresponding linear absorption spectrum in Figure shows very little broadening and a clear vibronic shoulder. The addition of the four methanol molecules that form peripheral H-bonds red-shifts the maximum by 0.014 eV (see section S8), but produces very little change in the spectral density or the shape or width of the absorption spectrum compared to the chromophore-only spectrum. In fact, measuring the full-width half-max (FWHM), which for these spectra only encompasses the 0-0 peak and not the vibronic shoulder, the peripheral solvent leads to a smaller value (0.039 eV FWHM) compared to the chromophore only spectrum (0.042 eV FWHM), showing that these strong H-bonds formed with the methanol solvent do not lead to inhomogeneous spectral broadening and in fact make the chromophore slightly more rigid. In contrast, if we replace those four H-bonding methanol solvent molecules with the four closest solvent molecules in the axial region of the chromophore that interact more strongly with the π-system of CV + , there is a significant increase in the intensity of the low-frequency region of the spectral density and the absorption spectrum becomes significantly broader (0.137 eV FWHM), nearly as broad as the spectrum with the full MM solvation shell that includes more than 1600 solvent molecules (0.148 eV FWHM). Compared to the spectrum generated from the chromophoreonly snapshots, the spectrum generated with the four axial solvent molecules blue shifts by 0.021 eV, whereas the full MM solvent region blue shifts by 0.030 eV. Including just the one solvent molecule that forms the axial H-bond at ∼40 ps into the trajectory, we see that the spectral density and the linear absorption spectrum are very similar to those generated with four solvent molecules (0.126 eV FWHM). Upon close approach and formation of the axial H-bond, this one solvent molecule clearly has an immense effect on the spectral broadening.