Quantum Dynamical Simulations as a Tool for Predicting Photoinjection Mechanisms in Dye-Sensitized TiO2 Solar Cells.

On the basis of a time-dependent self-consistent density functional tight-binding (TD-DFTB) approach, we present a novel method able to capture the differences between direct and indirect photoinjection mechanisms in a fully atomistic picture. A model anatase TiO2 nanoparticle (NP) functionalized with different dyes has been chosen as the object of study. We show that a linear dependence of the rate of electron injection with respect to the square of the applied field intensity can be viewed as a signature of a direct electron injection mechanism. In addition, we show that the nature of the photoabsorption process can be understood in terms of orbital population dynamics occurring during photoabsorption. Dyes involved in both direct (type-I) and indirect (type-II) mechanisms were studied to test the predictive power of this method.