A-Site Doping Promotes CO₂ Activation and Prolongs Charge Carrier Lifetimes in SrTiO₃: Insight from Quantum Dynamics

Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO₂ activation and charge carrier lifetimes in SrTiO₃(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO₂ on SrTiO₃ surfaces, which is beneficial for promoting CO₂ activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO₂ near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO₂ LUMO. Importantly, A-site doping causes a significant nonadiabatic coupling reduction and prolongs the charge recombination time by a factor of 1.86 compared to the pristine STO. Our study clarifies the influencing mechanism of A-site doping on CO₂ activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.