Determining the appropriate exchange-correlation functional for time-dependent density functional theory studies of charge-transfer excitations in organic dyes

UV-Vis spectra are calculated using time-dependent density functional theory for several organic dyes – 4-(N, N-dimethylamino) benzonitrile, alizarin, squaraine, polyene-linker dyes, oligothiophene-containing coumarin dyes (NKX series) and triphenylamine-donor dyes. Most of these dyes (except, for the first two) or their derivatives are considered to be promising organic dyes for dye-sensitized solar cells. An accurate description of the photophysics of such dyes is imperative for understanding and creating better dyes. To this end, we studied the dyes within several approximations to the exchange-correlation functional. The chosen functionals – PBE, M06L, B3LYP, M06, CAM-B3LYP, and wB97 – represent the various classes of approximations that are currently being used to study material properties. From amongst the six approximations studied here, CAM-B3LYP outperformed the others in its description of charge-transfer excitations in most (though, not all) of the dyes. This study shows why it is difficult to choose a particular functional a priori, especially when starting out with a new dye for solar cell application. A possible way to judge the fitness of an approximation is used in this work and it is shown to provide a good quantitative guideline for subsequent research in this field.