TD-DFT investigation of D-π-A organic dyes with thiophene moieties as π-spacers for use as sensitizers in DSSCs.

The geometrical, conformational, and electronic properties of a series of D-π-A metal-free dyes designed for use as sensitizers in DSSCs were studied using DFT and TD-DFT methods. A substituted triphenylamine moiety was used as the donor group and 2-cyanoacrylic acid as the acceptor group in these dyes. They also contained conjugated bridging π-linker groups containing two or more thiophene rings to enhance the intramolecular charge transfer. The B3LYP, M06-HF, ωB97XD and CAM-B3LYP functionals were utilized in combination with the 6-31G(d,p) basis set for the calculations. The dye solvation process was taken into account via the polarizable continuum model. To rationalize the relationships between dye structure and the photochemical properties of the dyes when used as sensitizers in DSSCs, the vertical excitation energies, the light-harvesting efficiencies, the free-energy changes during the process of injecting an electron into the surface of a TiO2 nanocrystalline semiconductor, and the open-circuit potentials were calculated for all of the dyes in the solvent THF using the above methods. The results of these computations are discussed and compared with the available corresponding experimental data.