Many-Body Quantum Chemistry Framework for Catalysis on Metallic Surfaces
Abstract
Electrocatalytic and thermocatalytic reactions on metal surfaces are crucial processes for converting inert molecules into fuels and value-added chemicals. Computational modeling plays an essential role in understanding catalytic reaction mechanisms at molecular level, but its predictive power has been hindered by uncontrolled errors in underlying quantum mechanical methods. In this proposal, we will create a many-body electronic structure toolbox to tackle challenges in simulating catalytic reactions on metallic surfaces. Our goal is to accurately describe molecular adsorption as well as chemical bond breaking and forming on surfaces, while properly treating possible effects of solvent, electrolyte, electric field, and temperature. This proposal consists of three objectives. First, we will develop a quantum embedding method to enable high level quantum chemical simulation of electrocatalytic reactions at constant electrode potential, with two levels of treatments of solvent and electrolyte effects. Specifically, we will implement new numerical algorithms for treating complex electronic structure in electrified metallic interfaces. Second, we will formulate a multireference Green s function theory suitable for computing bond dissociation barriers on metal surfaces. Third, we will apply our developed tools to investigate two challenging catalytic reactions of broad interest- electrochemical CO2 reduction on copper surfaces and propane dehydrogenation on single atom alloys. We anticipate that our work will provide a more reliable computational platform for studying the role of surfaces, defects, electric field, and liquid phase environment in catalytic reactions and exploring new strategies to design and control heterogeneous catalysis on metallic surfaces.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Feb 06, 2025
- Source ID
- FA95502410096
Entities
People
- Tianyu Zhu
Organizations
- Air Force Office of Scientific Research
- United States Air Force
- Yale University