This presentation considers theoretical investigations of dye-sensitized solar cells (DSSC). Theoretical methods were applied to investigate the interactions between titanium dioxide nanoparticles and sensitizers. The ONIOM model was used to obtain the geometries of different conformers of dye molecules with TiO2 and their binding energies. TD-DFT calculations were carried out to obtain the absorption spectra and the relative orbital energy levels of sensitizers and TiO2. The electronic couplings between different sensitizers and TiO2 were calculated using the fragment charge difference method. The redox potentials of the sensitizers are calculated to complete the full working cycle of a DSSC. We observed that the -COOH group is not the only possible binding site, and the sensitizers are more likely to be adsorbed horizontally on the TiO2 surface instead of being perpendicular to the surface having the -COOH group as a linker. The TiO2 nanoparticle was found to have minor influence on the absorptions of the sensitizers with the spectra shift smaller than 0.2 eV. TiO2 has more influence on the absorptions of softer and larger molecules because the interactions between sensitizers and TiO2 twist the conjugated chromophore structures. Compared to the neutral form, the deprotonated anion conformers of the sensitizers have larger binding energy and lower LUMO level against conduction band of TiO2. The gap between the LUMO of sensitizers and conduction band edge of TiO2 might indicate the coupling strength between the sensitizers and TiO2. Several binding groups have shown promising properties for interacting with the TiO2 nanoparticle and generally deprotonated anion forms of the dyes were strongly bonded to the TiO2 nanoparticle. The model and associated calculated results provide close agreement with experimental data and give crucial atomistic information of the relevant processes in dye-sensitized solar cells.
Dye-sensitized solar cells, Density functional calculations, Charge transport, UV-Vis absorption, Redox potentials