Computing redox potentials for dyes used in p-type dye-sensitized solar cells

Using density functional theory, we evaluate the redox potentials of inorganic dyes (hole injectors) used in the p-type dye sensitized solar cells. First, the theoretical level has been benchmarked for a prototypical case, by carefully considering all aspects of the model (basis set, pseudopotential, functional, solvent model, and thermodynamic cycle). This allowed to pinpoint a simple yet efficient approach providing theoretically converged values. In a second step, our results are compared to available experimental data for a series of recently synthesized ruthenium dyes differing by their anchoring group. As most theoretical investigations up to now have been focussed on n-type dyes and therefore on oxidation potentials, the proposed approach is a step toward a more rational design of both p-type and tandem dye-sensitized solar cell devices. (C) 2012 Wiley Periodicals, Inc.