(304b) Quantum Mechanical Description of Excited-State Heterogeneous Catalysis Via Embedded Correlated Wavefunction Methods

Nanoplasmonics is recognized to be potentially transformative for the field of heterogeneous catalysis. Localized surface plasmon resonances (LSPRs) can greatly influence chemical processes occurring on the metal catalysts’ surfaces, however the mechanism of enhancement is yet to be understood. First-principles quantum mechanics modeling is a widely used tool to understand heterogeneous catalysis, however, “garden-variety” density functional theory (DFT) is not suitable for the accurate description of such excited-state phenomena. Additionally DFT is known to have poor predictive ability when it comes to charge-transfer and bond dissociation processes. We thus employ embedded correlated wavefunction methods¹ (e.g., multi-configurational second order perturbation theory embedded in a density-functional-derived embedding potential) to explore the feasibility of light-driven catalysis on metallic nanoparticles. We evaluate if local electronic excitations (with energies at or below the LSPR frequency) centered at the surface reaction sites, can enable overcoming energy barriers for reactions that are otherwise kinetically forbidden to proceed in the ground state. N₂ dissociation on Fe- and Mo-doped Au(111) surfaces and CH₄activation on Ru-doped Cu(111) will be presented as examples.

[1] F. Libisch, C. Huang, and E. A. Carter, Acc. Chem. Res., 47, p. 2768 (2014).