Excitation-Wavelength-Dependent Charge-Carrier Lifetime in Hematite: An Insight from Nonadiabatic Molecular Dynamics

Experiments have reported that the photoexcited carrier lifetime in α-Fe₂O₃ has a significant excitation-wavelength dependence but leave the physical mechanism unresolved. In this work, we rationalize the puzzling excitation-wavelength dependence of the photoexcited carrier dynamics in Fe₂O₃ by performing nonadiabatic molecular dynamics simulation based on the strongly constrained and appropriately normed functional, which accurately describes the electronic structure of Fe₂O₃. Photogenerated electrons with lower-energy excitation relax fast in the t_2g conduction band within about 100 fs, while the photogenerated electrons with higher-energy excitation undergo first a slower interband relaxation from the e_g lower state to the t_2g upper state on a time scale of 135 ps, followed by the much faster t_2g intraband relaxation. This study provides insight into the experimentally reported excitation-wavelength dependence of the carrier lifetime in Fe₂O₃ and a reference for regulating photogenerated carrier dynamics in transition-metal oxides through the light excitation wavelength.