Ab initio investigation of the n→π* transitions in thiocarbonyl dyes

The n -> pi* transitions in more than 100 thiocarbonyl dyes have been calculated with an ab initio procedure relying on the combination of time-dependent density functional theory (TD-DFT) for evaluating excited states and the polarizable continuum model (PCM) for modeling the bulk solvent effects on both the geometrical and electronic structures. Two hybrid functionals (B3LYP and PBE0) and several basis sets, some including f polarization functions, have been used. B3LYP provides the most accurate raw estimates, but once simple linear regression is performed, both functionals give similar results with a small advantage for PBE0. By use of the latter, the mean absolute deviation with respect to experiment is limited to 0.06 eV whereas less than 20% of the estimates differ from absorption data by more than 0.10 eV. To assess the validity limits of our model, compounds containing multiple C=S chromophores have also been considered.