First-principles Investigation of the Catalytic Cycle for Lehn’s Catalyst at Silicon Surfaces

Predicting the CO₂ reduction catalytic cycle of molecular catalyst at the surface of photo-absorbing semiconductor materials is a significant challenge for realizing solar-to-fuel technology. While first-principles calculations such as Density Functional Theory (DFT) have become a workhorse for investigating complex heterostructures, advanced methodologies are needed to model the energy level alignment between molecules and semiconductor surfaces in order to predict the charge transfer at the interface. Using many-body perturbation theory based on Green’s function, which includes the dynamical screening effects of an electron from the surrounding electrons in the system, the GW calculation is a promising first-principles method that goes beyond the Kohn-Sham single-particle description given by DFT. We utilize this approach to better understand the mechanism underlying the catalytic cycle of Lehn’s catalyst for CO₂ reduction at silicon surfaces, pursued in the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE).