A‑Site\nDoping Promotes CO<sub>2</sub> Activation\nand Prolongs Charge Carrier Lifetimes in SrTiO<sub>3</sub>: Insight\nfrom Quantum Dynamics

Using time-dependent density functional theory and nonadiabatic\nmolecular dynamics, we systematically investigated the effect of A-site\ndoping on the CO<sub>2</sub> activation and charge carrier lifetimes\nin SrTiO<sub>3</sub>(STO). Our simulations revealed that A-site doping\nsignificantly enhances the chemical adsorption of CO<sub>2</sub> on\nSrTiO<sub>3</sub> surfaces, which is beneficial for promoting CO<sub>2</sub> activation. Moreover, we found that A-site doping can efficiently\nstabilize the lowest unoccupied molecular orbital (LUMO) of CO<sub>2</sub> near the conduction band minimum of STO, promoting the photogenerated\nelectron transfer from the conduction band of STO to the CO<sub>2</sub> LUMO. Importantly, A-site doping causes a significant nonadiabatic\ncoupling reduction and prolongs the charge recombination time by a\nfactor of 1.86 compared to the pristine STO. Our study clarifies the\ninfluencing mechanism of A-site doping on CO<sub>2</sub> activation\nand charge carrier lifetimes and suggests important principles for\nthe design of high-performance photocatalytic semiconductors.