Quantum-Computational Investigation of Non-adiabatic Light-Matter Coupling Effects on Catalytic Surface Reactions

Background: The control of chemical reactions at the quantum level represents a major frontier in catalysis. Strong light-matter coupling, where molecular electronic states hybridize with confined electromagnetic fields to form polaritons, offers a novel mechanism to reshape reaction potential energy surfaces. This non-adiabatic phenomenon provides a theoretical pathway to alter catalytic activity without changing the chemical composition of the catalyst. Aim: This study aimed to perform a quantum-computational investigation to quantify the effects of non-adiabatic light-matter coupling on the activation barrier of a model catalytic surface reaction. Methodology: A multi-scale computational model, Q-LightMat, was employed, integrating quantum electrodynamics with density functional theory. The simulations modeled a catalytic surface within an optical cavity to calculate the ground, excited, and polaritonic potential energy surfaces. Results: The simulation demonstrated the formation of distinct lower and upper polariton energy surfaces resulting from strong coupling with a 2.5 eV cavity mode. This coupling induced a significant catalytic effect, reducing the reaction activation barrier from 1.372 eV on the ground state to 1.243 eV on the lower polariton surface, a net reduction of 0.129 eV. The active learning pipeline used to accelerate the calculations converged with high accuracy, achieving a final force Mean Absolute Error of 0.064. Conclusion: Strong light-matter coupling provides a viable non-classical pathway to catalytically enhance surface reactions by lowering activation barriers. Future Recommendation: Future investigations should incorporate dynamic thermal fluctuations and environmental decoherence to evaluate the robustness of polaritonic effects under more realistic catalytic conditions.