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A first-principles study of stability of surface confined mixed metal oxides with a corundum structure (Fe2O3, Cr2O3, V2O3)

Summary

This PCCP study uses first-principles (DFT) methods to examine stability of surface-confined mixed oxides with corundum-related structure, focusing on Fe₂O₃, Cr₂O₃, and V₂O₃ combinations as ultrathin films on a support (details in the article). The motivation is that two-dimensional / surface-confined oxides can have chemistry distinct from bulk-like oxides—relevant to catalysis and surface science where termination, epitaxial strain, and lateral confinement shift oxide stoichiometry. Adri C. T. van Duin is included among coauthors, connecting the work to the group’s broader oxide interface interests even though the primary engine here is DFT, not ReaxFF MD. The ingested file is an RSC galley/proof (c8cp00154e header). Surface alloys and mixed terminations are evaluated to show how local composition on the support can stabilize motifs that would be high-energy in bulk corundum analogues.

Methods

  • DFT total-energy workflows on surface-confined Fe₂O₃, Cr₂O₃, and V₂O₃ (and mixed) corundum-structure films on a support, comparing candidate terminations and configurations (see Computational Details and ESI in the version-of-record), including relaxation protocols that map relative energies of mixed versus endmember terminations.
  • Electronic structure: DOS-style analyses in the article connect stability trends to d-band features where reported.

Static QM details (version-of-record alignment). This corpus slug points to an RSC galley/proof PDF for the same PCCP work as 2018jonayat-physical-che-first-principles-study (DOI 10.1039/c8cp00154e). Functional: PBE + Hubbard U on Fe, Cr, V 3d states as in the published Computational Details. Basis / code: plane-wave PAW DFT (VASP-style workflow per article). k-point sampling: Monkhorst–Pack k-point meshes for slabs and bulk references. Structures: relaxed corundum (0001) surface-confined films and Fe-doped V\(_2\)O\(_3\) terminations. Dispersion: N/A — explicit DFT-D correction not summarized here; confirm in the VOR PDF if applicable. Pathways: N/A — NEB not the headline method—surface energies and μ\(_O\) diagrams drive the conclusions.

Findings

Outcomes. Mixed M\(_x\)O\(_y\) terminations on the support can be thermodynamically preferred over bulk-like corundum fragments, shifting oxidation/reduction motifs at the interface.

Comparisons. Experimental surface-science signatures in the article benchmark the DFT phase boundaries for termination and reduction.

Sensitivity. Oxygen chemical potential (linked to T and p\(_{\mathrm{O_2}}\) via the article’s conventions) and Fe doping level move predicted segregation and termination stability.

Corpus honesty. Prefer 2018jonayat-physical-che-first-principles-study for VOR pagination; this galley pdf_path may differ in page numbers—cross-check figures before citing locators.

Limitations

  • DFT functional and hubbard / dispersion choices affect oxide energetics; check sensitivity for quantitative comparisons.
  • Proof PDF may differ slightly from the final typeset version in pagination or minor typography.

Relevance to group

van Duin coauthorship on a DFT-forward oxide stability paper adjacent to reactive FF development for similar chemistries.

Citations and evidence anchors

  • DOI: https://doi.org/10.1039/C8CP00154E (manuscript id C8CP00154E on the proof header; confirm against your library resolver if needed).

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