The calculations with TD-ωB97XD show that, when using the PCM model for ethanol, the energies are shifted by approximately 0.1-0.3 eV, except for the highest singlet state considered (S 5 ), where the shift exceeds 0.5 eV. In Table , the vertical excitations obtained with RI-CC2 and MS-CASPT2 were calculated considering ethanol as the solvent, using the COSMO and PCM approaches, respectively. Comparing the excited state energies in the solution, we notice that the MS-CASPT2 S 1 ππ * state has ∼1 eV and 0.6 eV lower energy compared to the TD-ωB97XD and RI-CC2 energies, respectively. The dark nπ * states (S 2 and S 3 ) energies are overestimated for ∼0.5 eV at the TD-ωB97XD level, whereas the RI-CC2