Alignment of the dye’s molecular levels with the TiO2band edges in dye-sensitized solar cells: a DFT–TDDFT study

We present a theoretical study of the lineup of the LUMO of Ru(II)-polypyridyl (N3 and N719) molecular dyes with the conduction band edge of a TiO2 anatase nanoparticle. We use density functional theory (DFT) and the Car–Parrinello scheme for efficient optimization of the dye–nanoparticle systems, followed by hybrid B3LYP functional calculations of the electronic structure and time-dependent DFT (TDDFT) determination of the lowest vertical excitation energies. The electronic structure and TDDFT calculations are performed in water solution, using a continuum model. Various approximate procedures to compute the excited state oxidation potential of dye sensitizers are discussed. Our calculations show that the level alignment for the interacting nanoparticle–sensitizer system is very similar, within about 0.1 eV, to that for the separated TiO2 and dye. The excellent agreement of our results with available experimental data indicates that the approach of this work could be used as an efficient predictive tool to help the optimization of dye-sensitized solar cells.