Nonequilibrium Electronic Response Modes Link Excitation Energy to Catalytic Reactivity
Year: 2026
Type: preprint
Abstract: Illumination can promote or inhibit catalytic reactions, yet the origin of their excitation-energy dependence remains unclear. Here, constrained ΔSCF calculations and spin- and k-resolved wavefunction-overlap tracking are used to follow nonequilibrium electronic configurations across four excitation-energy intervals along H2-dissociation pathways at doped Cu/ZnO interfaces. The preferred pathway switches from final-state-referenced configurations at low excitation energies to initial-state-referenced configurations at higher energies, with dopant-dependent crossover energies and nonmonotonic barrier responses. Metal-site dopants regulate reactivity primarily through excitation-induced reconstruction of collective metal-H bonding, whereas support-site dopants act through pathway-dependent interfacial spin redistribution. Neither excitation energy nor the magnitude of charge, bonding, or spin redistribution alone universally predicts catalytic promotion; the response depends on its direction, localization, and differential coupling to the initial and transition states. Application to Ag-mediated O2 dissociation further demonstrates that population-dependent interfacial reorganization, rather than net adsorbate charge alone, controls bond activation.
Source: ChemRxiv
Authors: Mengru Li, Hao Wang, Hui Yin
Institution: Lanzhou University
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7204993968