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Title: MnNiO3 revisited with modern theoretical and experimental methods

Abstract

MnNiO3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photocatalyst. However, there is no experimental report on critical quantities such as the band gap or bulk modulus. Recent theoretical predictions with standard functionals such as LDA+U and HSE show large discrepancies in the band gaps (about 1.23 eV), depending on the nature of the functional used. Hence there is clearly a need for an accurate quantitative prediction of the band gap to gauge its utility as a photocatalyst. In this work, we present a diffusion quantum Monte Carlo study of the bulk properties of MnNiO3 and revisit the synthesis and experimental properties of the compound. We predict quasiparticle band gaps of 2.0(5) eV and 3.8(6) eV for the majority and minority spin channels, respectively, and an equilibrium volume of 92.8 Å3, which compares well to the experimental value of 94.4 Å3. A bulk modulus of 217 GPa is predicted for MnNiO3. As a result, we rationalize the difficulty for the formation of ordered ilmenite-type structure with specific sites for Ni and Mn to be potentially due to the formation of antisite defects that form during synthesis, which ultimatelymore » affects the physical properties of MnNiO3.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1407769
Alternate Identifier(s):
OSTI ID: 1408159
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Dzubak, Allison L., Mitra, Chandrima, Chance, Michael, Kuhn, Stephen, Jellison, Jr., Gerald E., Sefat, Athena S., Krogel, Jaron T., and Reboredo, Fernando A. MnNiO3 revisited with modern theoretical and experimental methods. United States: N. p., 2017. Web. doi:10.1063/1.5000847.
Dzubak, Allison L., Mitra, Chandrima, Chance, Michael, Kuhn, Stephen, Jellison, Jr., Gerald E., Sefat, Athena S., Krogel, Jaron T., & Reboredo, Fernando A. MnNiO3 revisited with modern theoretical and experimental methods. United States. doi:https://doi.org/10.1063/1.5000847
Dzubak, Allison L., Mitra, Chandrima, Chance, Michael, Kuhn, Stephen, Jellison, Jr., Gerald E., Sefat, Athena S., Krogel, Jaron T., and Reboredo, Fernando A. Fri . "MnNiO3 revisited with modern theoretical and experimental methods". United States. doi:https://doi.org/10.1063/1.5000847. https://www.osti.gov/servlets/purl/1407769.
@article{osti_1407769,
title = {MnNiO3 revisited with modern theoretical and experimental methods},
author = {Dzubak, Allison L. and Mitra, Chandrima and Chance, Michael and Kuhn, Stephen and Jellison, Jr., Gerald E. and Sefat, Athena S. and Krogel, Jaron T. and Reboredo, Fernando A.},
abstractNote = {MnNiO3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photocatalyst. However, there is no experimental report on critical quantities such as the band gap or bulk modulus. Recent theoretical predictions with standard functionals such as LDA+U and HSE show large discrepancies in the band gaps (about 1.23 eV), depending on the nature of the functional used. Hence there is clearly a need for an accurate quantitative prediction of the band gap to gauge its utility as a photocatalyst. In this work, we present a diffusion quantum Monte Carlo study of the bulk properties of MnNiO3 and revisit the synthesis and experimental properties of the compound. We predict quasiparticle band gaps of 2.0(5) eV and 3.8(6) eV for the majority and minority spin channels, respectively, and an equilibrium volume of 92.8 Å3, which compares well to the experimental value of 94.4 Å3. A bulk modulus of 217 GPa is predicted for MnNiO3. As a result, we rationalize the difficulty for the formation of ordered ilmenite-type structure with specific sites for Ni and Mn to be potentially due to the formation of antisite defects that form during synthesis, which ultimately affects the physical properties of MnNiO3.},
doi = {10.1063/1.5000847},
journal = {Journal of Chemical Physics},
number = 17,
volume = 147,
place = {United States},
year = {2017},
month = {11}
}

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