The origin of metallic conductivity in Pt3O4 : a first principles study

Peeketi, Akhil Reddy; Rekhi, Lavie; Muñoz, Alexander Reed; Jayan, Rahul; Holby, Edward F.; Uberuaga, Blas P.; Jones, Travis Elliot Lloyd

doi:10.1088/2516-1075/ae2a8a

Title: The origin of metallic conductivity in Pt₃O₄ : a first principles study

Journal Article · Mon Jan 19 00:00:00 UTC 2026 · Electronic Structure

DOI: https://doi.org/10.1088/2516-1075/ae2a8a · OSTI ID:3017792

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

The platinum oxide Pt₃O₄ exhibits metallic conductivity even though it contains square-planar PtO4 units, which in related oxides such as PtO are usually associated with insulating behavior. To identify the electronic origin of this anomalous metallicity, we performed a comprehensive first-principles study using the PBE and r²SCAN functionals together with Hubbard U corrections and spin-orbit coupling (SOC). Structural benchmarks show that r²SCAN with SOC and a moderate U value (<4 eV) reproduces the experimental lattice constants and formation enthalpy, whereas larger U values (~8 eV) destabilize the cubic structure. Across all functionals and U values considered in this work, Pt₃O₄ remains metallic. Analyses of the projected density of states, band structures, charge-density isosurfaces, and bonding characteristics demonstrate that the dominant contribution to the metallic character originates from delocalized Pt–O–Pt hybridized antibonding states at the Fermi level. Direct Pt–Pt interactions are present but contribute less strongly to the conductivity. Bader charge analysis reveals only weak Pt charge disproportionation, consistent with mixed Pt^II/Pt^III character, and a small charge-transfer energy that prevents localization of the Pt 5d electrons even at elevated U. In contrast, PtO develops a Mott or charge-transfer gap under modest U despite having the same PtO₄ coordination environment. These findings demonstrate that persistent Pt–O–Pt covalency is the primary driver of metallicity in Pt₃O₄ and support the view that this phase can remain conductive under oxygen reduction and oxygen evolution reaction conditions in fuel cell and electrolyzer environments.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 3017792

Report Number(s):: LA-UR--25-29237; 10.1088/2516-1075/ae2a8a; 2516-1075

Journal Information:: Electronic Structure, Journal Name: Electronic Structure Journal Issue: 1 Vol. 8; ISSN 2516-1075

Publisher:: IOP ScienceCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Pt3O4
crystal orbital Hamilton population (COHP)
density functional theory (DFT)
electrocatalysis
electronic conductivity
platinum oxides
projected density of states (PDOS)

Title: The origin of metallic conductivity in Pt3O4 : a first principles study

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Title: The origin of metallic conductivity in Pt₃O₄ : a first principles study