Time-dependent density functional theory determination of the absorption spectra of naphthoquinones

The electronic excited states of solvated 1,4-naphthoquinone dyes have been determined using time-dependent density functional theory (TD-DFT) combined with the polarizable continuum model (PCM). It turns out that the 6-311+G(2d,p) and 6-311G(d,p) basis sets provide, respectively, almost perfectly converged excitation spectra, and geometries. Using the PBE0 hybrid functional, we obtain a valuable correlation between PCM-TD-DFT and experimental transitions in both the ultraviolet and the visible parts of the absorption spectra. Indeed, for the 69 1,4-naphthoquinone studied transitions, the mean signed/absolute deviation are limited to +3.6 nm (−0.048 eV)/9.5 nm (0.100 eV). Qualitative correlations between the geometrical, vibrational and electronic characteristics has been established. In addition, the spectra of several 1,2-naphthoquinones have been considered.