First-principles study of crystal and electronic structure of rare-earth cobaltites

M. Topsakal, C. Leighton, R. M. Wentzcovitch

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Using density functional theory plus self-consistent Hubbard U (DFT + Usc) calculations, we have investigated the structural and electronic properties of the rare-earth cobaltites RCoO3 (R = Pr - Lu). Our calculations show the evolution of crystal and electronic structure of the insulating low-spin RCoO3 with increasing rare-earth atomic number (decreasing ionic radius), including the invariance of the Co-O bond distance (dCo-O), the decrease of the Co-O-Co bond angle (Θ), and the increase of the crystal field splitting (ΔCF) and band gap energy (Eg). Agreement with experiment for the latter improves considerably with the use of DFT + Usc and all trends are in good agreement with the experimental data. These trends enable a direct test of prior rationalizations of the trend in spin-gap associated with the spin crossover in this series, which is found to expose significant issues with simple band based arguments. We also examine the effect of placing the rare-earth f-electrons in the core region of the pseudopotential. The effect on lattice parameters and band structure is found to be small, but distinct for the special case of PrCoO3 where some f-states populate the middle of the gap, consistent with the recent reports of unique behavior in Pr-containing cobaltites. Overall, this study establishes a foundation for future predictive studies of thermally induced spin excitations in rare-earth cobaltites and similar systems.

Original languageEnglish (US)
Article number244310
JournalJournal of Applied Physics
Issue number24
StatePublished - Jun 28 2016

Bibliographical note

Funding Information:
This work was supported primarily by the NSF MRSEC under Award Nos. DMR-0819885 and DMR-1420013. R.M.W. was also supported by NSF/EAR 1319361. C.L.'s contribution was supported by the DOE through DE-FG02-06ER46275. We acknowledge the fruitful discussions with Dr. Koichiro Umemoto and Dr. Han Hsu. Part of the computational resources has been provided through the Extreme Science and Engineering Discovery Environment (XSEDE), supported by National Science Foundation Grant No. ACI-1053575.

Publisher Copyright:
© 2016 Author(s).

How much support was provided by MRSEC?

  • Primary

Reporting period for MRSEC

  • Period 3

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