Ultrafast dynamics of solvated electrons at anatase TiO₂/H₂O interface

Solvated electrons are known to be the lowest energy charge transfer pathways at oxide/aqueous interface and the understanding of the electron transfer dynamics at the interface is fundamental for photochemical and photocatalytic processes. Taking anatase TiO₂/H₂O interface as a prototypical system, we perform time-dependent ab initio nonadiabatic molecular dynamics calculations to study the charge transfer dynamics of solvated electrons. For the static electronic properties, we find that the dangling H atoms can stabilize solvated electrons. A solvated electron band can be formed with one monolayer H₂O adsorption. The energies of the solvated electron band minimum (SEBM) decrease when H₂O adsorbs dissociatively. Moreover, the surface oxygen vacancies are also helpful for stabilizing the solvated electron band. For the dynamics behaviour, we find that the ultrafast charge transfer from SEBM to anatase TiO₂ (1 0 1) surface at 100 K is mainly contributed by nonadiabatic mechanism. Comparing with rutile TiO₂ (1 1 0) surface, the lifetime of solvated electron on anatase TiO₂ (1 0 1) surface is longer, suggesting a better photocatalytic properties. Our results provide essential insights into the understanding of the charge transfer dynamics and the possible photocatalytic mechanism at oxide/aqueous interface.