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Title: Electronic properties of doped and defective NiO: A quantum Monte Carlo study

Abstract

NiO is a canonical Mott (or charge-transfer) insulator and as such is notoriously difficult to describe using density functional theory (DFT) based electronic structure methods. Doped Mott insulators such as NiO are of interest for various applications but rigorous theoretical descriptions are lacking. Here, we use quantum Monte Carlo methods, which very accurately include electron-electron interactions, to examine energetics, charge- and spin-structures of NiO with various point defects, such as vacancies or substitutional doping with potassium. The formation energy of a potassium dopant is significantly lower than for a Ni vacancy, making potassium an attractive monovalent dopant for NiO. We compare our results with DFT results that include an on-site Hubbard U (DFT+U) to account for correlations and find relatively large discrepancies for defect formation energies as well as for charge and spin redistributions in the presence of point defects. Finally, it is unlikely that single-parameter fixes of DFT may be able to obtain accurate accounts of anything but a single parameter, e.g., band gap; responses that, maybe in addition to the band gap, depend in subtle and complex ways on ground state properties, such as charge and spin densities, are likely to contain quantitative and qualitative errors.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [1];  [4]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Northwestern Univ., Evanston, IL (United States). Inst. for Science and Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1416980
Alternate Identifier(s):
OSTI ID: 1416430; OSTI ID: 1422575
Grant/Contract Number:  
AC02-06CH11357; AC05-00OR22725; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 7; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Quantum Monte Carlo; Density Functional Theory; DFT; Point Defects

Citation Formats

Shin, Hyeondeok, Luo, Ye, Ganesh, Panchapakesan, Balachandran, Janakiraman, Krogel, Jaron T., Kent, Paul R. C., Benali, Anouar, and Heinonen, Olle. Electronic properties of doped and defective NiO: A quantum Monte Carlo study. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.073603.
Shin, Hyeondeok, Luo, Ye, Ganesh, Panchapakesan, Balachandran, Janakiraman, Krogel, Jaron T., Kent, Paul R. C., Benali, Anouar, & Heinonen, Olle. Electronic properties of doped and defective NiO: A quantum Monte Carlo study. United States. doi:10.1103/PhysRevMaterials.1.073603.
Shin, Hyeondeok, Luo, Ye, Ganesh, Panchapakesan, Balachandran, Janakiraman, Krogel, Jaron T., Kent, Paul R. C., Benali, Anouar, and Heinonen, Olle. Thu . "Electronic properties of doped and defective NiO: A quantum Monte Carlo study". United States. doi:10.1103/PhysRevMaterials.1.073603. https://www.osti.gov/servlets/purl/1416980.
@article{osti_1416980,
title = {Electronic properties of doped and defective NiO: A quantum Monte Carlo study},
author = {Shin, Hyeondeok and Luo, Ye and Ganesh, Panchapakesan and Balachandran, Janakiraman and Krogel, Jaron T. and Kent, Paul R. C. and Benali, Anouar and Heinonen, Olle},
abstractNote = {NiO is a canonical Mott (or charge-transfer) insulator and as such is notoriously difficult to describe using density functional theory (DFT) based electronic structure methods. Doped Mott insulators such as NiO are of interest for various applications but rigorous theoretical descriptions are lacking. Here, we use quantum Monte Carlo methods, which very accurately include electron-electron interactions, to examine energetics, charge- and spin-structures of NiO with various point defects, such as vacancies or substitutional doping with potassium. The formation energy of a potassium dopant is significantly lower than for a Ni vacancy, making potassium an attractive monovalent dopant for NiO. We compare our results with DFT results that include an on-site Hubbard U (DFT+U) to account for correlations and find relatively large discrepancies for defect formation energies as well as for charge and spin redistributions in the presence of point defects. Finally, it is unlikely that single-parameter fixes of DFT may be able to obtain accurate accounts of anything but a single parameter, e.g., band gap; responses that, maybe in addition to the band gap, depend in subtle and complex ways on ground state properties, such as charge and spin densities, are likely to contain quantitative and qualitative errors.},
doi = {10.1103/PhysRevMaterials.1.073603},
journal = {Physical Review Materials},
issn = {2475-9953},
number = 7,
volume = 1,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

FIG. 2 FIG. 2: (a) DMC total energy of AFM type II NiO as function of time step. The dotted line indicates a quadratic fit. (b) DMC total energy of NiO as function 1/N , where N is the total number of atoms in the supercell. The dotted line indicates a simplemore » linear regression fit.« less

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