Local environment dependent GGA+U method for accurate thermochemistry of transition metal compounds

Muratahan Aykol, C. Wolverton

Research output: Contribution to journalArticlepeer-review

59 Scopus citations

Abstract

We present a framework to carry out highly accurate GGA+U thermochemistry calculations by deriving effective U values from experimental data. The U values predicted in this approach are applied to metal cations, and depend not only on (i) the chemical identity and the band to which the U correction is applied, but also on the local environment of the metal described by (ii) its oxidation state and (iii) the surrounding ligand. We predict such local environment dependent (LD) U values for the common oxidation states of 3d metals M= Ti, V, Cr, Mn, Fe, Co, and Ni in their oxides and fluorides. We implement the GGA/GGA+U mixing method [Jain Phys. Rev. B 84, 045115 (2011)PRBMDO1098-012110.1103/PhysRevB.84.045115] to establish the total energy compatibility among the GGA+U calculations involving M treated with different LD-U values. Using the presented framework, formation enthalpies of 52 transition metal bearing oxides (which are not used during the LD-U parametrization) are predicted with a remarkably small mean absolute error of ∼19 meV/atom, which is on the order of the experimental chemical accuracy. In addition, we present applications of the method in redox processes of important 3d-metal oxide and fluoride systems such as LixCoO2,LixV6O13,LixFeF3, and VO1.5+x, and show that LD-GGA+U can overcome several drawbacks of using constant-U values in conventional GGA+U.

Original languageEnglish (US)
Article number115105
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume90
Issue number11
DOIs
StatePublished - Sep 2 2014

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

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