Modeling opto-electronic properties of a dye molecule in proximity of a semiconductor nanoparticle

A general methodology is presented to model the opto-electronic properties of a dye molecule in the presence of a semiconductor nanoparticle (NP), a model system for the architecture of dye-sensitized solar cells. The method is applied to the L0 organic dye solvated with acetonitrile in the neighborhood of a TiO2 NP. The total reaction potential due to the polarization of the solvent and the metal oxide is calculated by extending the polarizable continuum model integral equation formalism. The ground state energy is computed by using density functional theory (DFT) while the vertical electronic excitations are obtained by time-dependent DFT in a state-specific corrected linear response scheme. We calculate the excited state oxidation potential (ESOP) for the protonated and deprotonated forms of the L0 dye at different distances and configurations with respect to the NP surface. The stronger renormalizations of the ESOP values due to the presence of the TiO2 nanostructure are found for the protonated dye, reaching a maximum of about −0.15 eV. The role of protonation effect is discussed in terms of the atomic Löwdin charges of the oxidized and reduced species. On the other hand, we observed a weak effect on the L0 optical excitation gap due to the polarization response of the NP.