Estimating Nonradiative Excited-State Lifetimes in Photoactive Semiconducting Nanostructures.

The time evolution of the exciton generated by light adsorption in a photocatalyst is an important feature that can be approached from full nonadiabatic molecular dynamics simulations. Here, a crucial parameter is the nonradiative recombination rate between the hole and the electron that form the exciton. In the present work, we explore the performance of a Fermi's golden rule-based approach on predicting the recombination rate in a set of photoactive titania nanostructures, relying solely on the coupling of the ground and first excited state. In this scheme the analysis of the first excited state is carried out by invoking Kasha's rule thus avoiding computationally expensive nonadiabatic molecular dynamics simulations and resulting in an affordable estimate of the recombination rate. Our results show that, compared to previous ones from nonadiabatic molecular dynamics simulations, semiquantitative recombination rates can be predicted for the smaller titania nanostructures, and qualitative values are obtained from the larger ones. The present scheme is expected to be useful in the field of computational heterogeneous photocatalysis whenever a complex and computationally expensive full nonadiabatic molecular dynamics cannot be carried out.