To assess the importance of symmetry breaking in understanding the optical properties CV, Kohn-Sham molecular orbitals, excited state energies and transition densities were computed for selected static configurations of the molecule. Optimized geometries and molecular orbitals were computed for the chromophore in vacuum using Gaussian, excited state energies and transition densities were computed using TeraChem. The ωb97x 68 functional with the 6-31+G* 69 basis set were used throughout for results presented in the main text, and detailed analysis of the dependence of lowlying excitation energies on DFT functional choice can be found in SI Sec. 5. Since CV is a cationic organic dye, calculations were performed both on the isolated chromophore and on the chromophore in the presence of a chloride counterion. In each case, the ground state geometry was optimized using density-functional theory (DFT) and the excited state energies were computed using full time-dependent DFT (TDDFT) in the linearresponse formalism. Transition densities for S 1 and S 2 were computed using TDDFT within the Tamm-Dancoff approximation.