DFT is used to treat the chromophore during QM/MM simulations and to parametrize the force field for classical MD, whereas TDDFT is used to model the excited states as discussed below. The excitation energies depend strongly on the degree of exact exchange in the density functional, with more exact exchange generally leading to higher excitation energies. In a previous study by Kostjukov that surveyed the performance of forty hybrid density functionals for simulating the absorption spectrum of the aqueously solvated cresyl violet cation, the range-separated CAM-B3LYP functional was one of the most accurate when comparing the energies of the simulated and experimental vibronic maxima, along with M06-2X and ω-B97XD functionals. The vibronic spectra generated from this same study produced a vibronic shoulder weaker than in the experimental spectrum, with the author noting that spectra generated using all 40 functionals had nearly the same shape. Indeed, our benchmark calculations of Franck-Condon vibronic spectra for CV + in a polarizable continuum model for methanol (see Figure ) show very similar vibronic lineshapes for CAM-B3LYP, M06-2X, and ω-B97XD, with M06-2X producing a slightly more narrow spectrum and ω-B97XD producing a slightly broader spectrum than CAM-B3LYP. We also show the vibronic spectrum generated by the LC-ωHPBE functional, which is broader than the other spectra, likely due to the larger value of the range-separation parameter (ω = 0.40 for LC-ωHPBE, ω = 0.20 for ω-B97XD). Because the CAM-B3LYP functional has yielded accurate vibronic spectral shapes in studies of other systems, we here use the CAM-B3LYP functional.