Nonequilibrium Electronic Response Modes Link Excitation Energy to Catalytic Reactivity
- 1Key Laboratory of Advanced Catalysis; State Key Laboratory of Natural Product Chemistry, College of Chemistry and Chemical Engineering
- 2Lanzhou University
- 3Yunnan Precious Metal Laboratory Co., Ltd.
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.
Related
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BibTeX
@misc{li2026nonequilibrium,
title = {{Nonequilibrium Electronic Response Modes Link Excitation Energy to Catalytic Reactivity}},
author = {Mengru Li and Hao Wang and Hui Yin},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008182/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008182/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Nonequilibrium Electronic Response Modes Link Excitation Energy to Catalytic Reactivity
AU - Mengru Li
AU - Hao Wang
AU - Hui Yin
PY - 2026
DA - 2026/09/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008182/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008182/v1
AB - 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.
ER -