A-Site Doping Promotes CO Activation and Prolongs Charge Carrier Lifetimes in SrTiO: 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 CO activation and charge carrier lifetimes in SrTiO(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO on SrTiO surfaces, which is beneficial for promoting CO activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO 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 CO activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.