Structure and Energetics of Dye-Sensitized NiO Interfaces in Water from Ab Initio MD and Large-Scale GW Calculations.

The energy-level alignment across solvated molecule/semiconductor interfaces is a crucial property for the correct functioning of dye-sensitized photoelectrodes, where, following the absorption of solar light, a cascade of interfacial hole/electron transfer processes has to efficiently take place. In light of the difficulty of performing X-ray photoelectron spectroscopy measurements at the molecule/solvent/metal-oxide interface, being able to accurately predict the level alignment by first-principles calculations on realistic structural models would represent an important step toward the optimization of the device. In this respect, dye/NiO surfaces, employed in p-type dye-sensitized solar cells, are undoubtedly challenging for ab initio methods and, also for this reason, much less investigated than the n-type dye/TiO