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oai:figshare.com:article/34021994 2026-09-29T08:05:08Z category_1 category_4 category_146 category_915 category_7 category_14 category_16 category_873 category_734 category_132 portal_63 item_type_6 month_year_09_2026

Out-of-Plane Strain Modulates Frontier-Orbital Splitting and Vibrational Wave Function Overlap at M–N₄ Single-Atom Catalytic Sites Adebola Omoyeni (25136021) Sayan Banerjee (8641302) Biophysics Biochemistry Space Science Physical Sciences not elsewhere classified Medicine Molecular Biology Physiology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified Infectious Diseases offering mechanistic insight local symmetry breaking learning feature selection centered frontier orbitals atom catalytic sites transfer kinetic descriptors nonzero curvature enhances 4 </ sub 2 </ sub proton vibrational overlap plane strain associated induced reactivity modulation catalytic sites vibrational responses – n results establish reduction reactions plane curvature geometric descriptor coupled electron coordination pocket Out-of-plane strain associated with nonzero curvature enhances the reactivity of M–N–C single-atom catalytic sites embedded in graphene toward electrochemical oxygen reduction as well as CO₂ reduction reactions. Here, by combining density functional theory calculations, quantized proton vibrational analysis, and machine-learning feature selection, we show that curvature-induced deformation drives coupled electronic-structure and vibrational responses at M–N₄ single-atom catalytic sites. Systematic comparison across signed curvature values for multiple metal–adsorbate combinations reveals two coupled consequences of deformation: (i) splitting of metal-centered frontier orbitals and local symmetry breaking of the M–N₄ coordination pocket, and (ii) modulation of the reactant–product proton vibrational wave function overlap, with implications for proton-transfer and proton-coupled electron-transfer kinetic descriptors. These results establish out-of-plane curvature as a geometric descriptor that simultaneously modulates adsorbate binding thermodynamics and proton vibrational overlap, offering mechanistic insight into out-of-plane-strain-induced reactivity modulation at catalytic sites. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/acs.jpcc.6c04789.s001 https://figshare.com/articles/journal_contribution/Out-of-Plane_Strain_Modulates_Frontier-Orbital_Splitting_and_Vibrational_Wave_Function_Overlap_at_M_N_sub_4_sub_Single-Atom_Catalytic_Sites/34021994 CC BY-NC 4.0