Abstract
Exploiting the availability of solar energy to produce valuable chemicals is imperative in our quest for a sustainable energy cycle. TiO(2) has emerged as an efficient photocatalyst, and as such its photochemistry has been studied extensively. It is well-known that polaronic defect states impact the activity of this chemistry. As such, understanding the fundamental excitation mechanisms deserves the attention of the scientific community. However, isolating the contribution of polarons to these processes has required increasingly creative experimental techniques and expensive theory. In this Perspective, we discuss recent advances in this field, with a particular focus on two-photon photoemission spectroscopy (2PPE) and density functional theory (DFT), and discuss the implications for photocatalysis.