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Orbital-driven superexchange engineering at molecule/antiferromagnetic-oxide interfaces

Shuangying Ma, Marco Marino*, and Guido Fratesi†

  • Physics Department Aldo Pontremoli, University of Milan, via Celoria 16, Milano 20133, MI, Italy

  • *Present address: TU Dortmund University, Otto-Hahn-Straße 4, 44227 Dortmund, Germany.
  • †Contact author: guido.fratesi@unimi.it
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Phys. Rev. B 113, 214407 – Published 1 June, 2026

DOI: https://doi.org/10.1103/33f3-z6rd

Abstract

Antiferromagnetic transition-metal oxides provide robust platforms for spintronic and magnonic applications, where control of magnetic exchange interactions is essential for tailoring spin dynamics. Molecular adsorption at organic/inorganic interfaces offers a promising route to chemically engineer these interactions. We investigate how molecular adsorption modifies surface superexchange interactions in antiferromagnetic transition-metal oxides. Using density functional theory+U calculations, we study prototypical interfaces formed by C60 and cobalt-tetraphenylporphyrin (CoTPP) adsorbed on NiO(001) and CoO(001) and extract exchange coupling constants J from broken-symmetry total-energy calculations mapped onto a Heisenberg model. For clean surfaces, we obtain J≈−30meV for NiO(001) and J≈−21meV for CoO(001). Upon molecular adsorption, the magnitude of J increases to −31/−32meV for NiO and to −27/−30meV for CoO, corresponding to enhancements up to 9meV for CoTPP/CoO(001). Orbital-resolved analysis reveals that the strengthening of superexchange correlates with a directional redistribution of charge within the transition-metal d manifold, characterized by a redistribution of charge involving enhanced occupation of in-plane σ and out-of-plane π-type orbitals aligned with the TM–O–TM and TM–molecule–TM superexchange pathways, accompanied by depletion of out-of-plane σ and in-plane π orbitals. While only two representative molecules and two oxides are considered here, the consistency of the observed trends across chemically distinct systems suggests that the proposed orbital-repopulation mechanism may apply more broadly to related organic/antiferromagnetic-oxide interfaces.

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Phys. Rev. B 113, 214407– Published 1 June, 2026
  • Received 12 December 2025
  • Revised 17 April 2026
  • Accepted 23 April 2026
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