Exploring the Possibility of Proton-Coupled Electron Transfer at Catalyst–Semiconductor Interfaces with Real-Time NEO-TDDFT

Understanding proton-coupled electron transfer (PCET) at molecule–semiconductor interfaces is crucial for unraveling the detailed mechanisms that drive solar-to-fuel conversion of CO₂. Building on our prior work on studying catalyst catalytic cycle of Lehn’s catalyst at silicon surfaces, we employ real-time nuclear–electronic orbital time-dependent density functional theory (RT-NEO-TDDFT) with Ehrenfest dynamics to investigate the possibility of PCET during the key stage of catalysis that allows for CO₂ reduction. This approach enables simultaneous quantum treatment of both electrons and selected protons, capturing nonadiabatic effects beyond the Born–Oppenheimer approximation.^1,2 These results, pursued within the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE), provide a dynamic, first-principles perspective on the elementary steps that govern catalytic CO₂ reduction at molecule-functionalized photoelectrodes.

1. Xu, J., Zhou, R., Li, T. E., Hammes-Schiffer, S., & Kanai, Y. (2024). Lagrangian formulation of nuclear–electronic orbital Ehrenfest dynamics with real-time TDDFT for extended periodic systems. The Journal of Chemical Physics, 161(19

2. Xu, J., Zhou, R., Blum, V., Li, T. E., Hammes-Schiffer, S., & Kanai, Y. (2023). First-principles approach for coupled quantum dynamics of electrons and protons in heterogeneous systems. Physical review letters, 131(23), 238002.