skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Valence and spin fluctuations in the Mn-doped ferroelectric BaTiO 3

Abstract

We study Mn substitution for BaTiO 3 with and without compensating oxygen vacancies using density functional theory (DFT) in combination with dynamical mean-field theory (DMFT). We find strong charge and spin fluctuations. Without compensating oxygen vacancies, the ground state is found to be a quantum superposition of two distinct atomic valences, $3d^4$ and $3d^5$. Introducing a compensating oxygen vacancy at a neighboring site reduces both charge and spin fluctuations due to the reduction of electron hopping from Mn to its ligands. As a consequence, valence fluctuations are reduced, and the valence is closely fixed to the high spin $3d^5$ state. Here we show that inclusion of charge and spin fluctuations is necessary to obtain an accurate ground state of transition metal-doped ferroelectrics.

Authors:
 [1];  [2];  [3]
  1. Yale Univ., New Haven, CT (United States). Dept. of Applied Physics; Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  2. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.; Ludwig Maximilian Univ., Munich (Germany). Dept. of Earth and Environmental Sciences
  3. 4Department of Physics, Rutgers University, Piscataway, New Jersey 08854, USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1544223
Grant/Contract Number:  
N00014-12-1-1038; N00014-14-1-0561; N00014-17-1-2768; ACI-1339804; DMR-1709229
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; Journal Issue: 7; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Mandal, Subhasish, Cohen, R. E., and Haule, K. Valence and spin fluctuations in the Mn-doped ferroelectric BaTiO3. United States: N. p., 2018. Web. doi:10.1103/PhysRevB.98.075155.
Mandal, Subhasish, Cohen, R. E., & Haule, K. Valence and spin fluctuations in the Mn-doped ferroelectric BaTiO3. United States. doi:10.1103/PhysRevB.98.075155.
Mandal, Subhasish, Cohen, R. E., and Haule, K. Wed . "Valence and spin fluctuations in the Mn-doped ferroelectric BaTiO3". United States. doi:10.1103/PhysRevB.98.075155. https://www.osti.gov/servlets/purl/1544223.
@article{osti_1544223,
title = {Valence and spin fluctuations in the Mn-doped ferroelectric BaTiO3},
author = {Mandal, Subhasish and Cohen, R. E. and Haule, K.},
abstractNote = {We study Mn substitution for BaTiO3 with and without compensating oxygen vacancies using density functional theory (DFT) in combination with dynamical mean-field theory (DMFT). We find strong charge and spin fluctuations. Without compensating oxygen vacancies, the ground state is found to be a quantum superposition of two distinct atomic valences, $3d^4$ and $3d^5$. Introducing a compensating oxygen vacancy at a neighboring site reduces both charge and spin fluctuations due to the reduction of electron hopping from Mn to its ligands. As a consequence, valence fluctuations are reduced, and the valence is closely fixed to the high spin $3d^5$ state. Here we show that inclusion of charge and spin fluctuations is necessary to obtain an accurate ground state of transition metal-doped ferroelectrics.},
doi = {10.1103/PhysRevB.98.075155},
journal = {Physical Review B},
number = 7,
volume = 98,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Self-consistent G W determination of the interaction strength: Application to the iron arsenide superconductors
journal, July 2010


Covalency in transition-metal oxides within all-electron dynamical mean-field theory
journal, August 2014


Bond- versus site-centred ordering and possible ferroelectricity in manganites
journal, November 2004

  • Efremov, Dmitry V.; van den Brink, Jeroen; Khomskii, Daniel I.
  • Nature Materials, Vol. 3, Issue 12
  • DOI: 10.1038/nmat1236

Magnetism in Mn-doped ZnO nanoparticles prepared by a co-precipitation method
journal, February 2006


Properties of Mn-Implanted BaTiO[sub 3], SrTiO[sub 3], and KTaO[sub 3]
journal, January 2003

  • Norton, D. P.; Theodoropoulou, N. A.; Hebard, A. F.
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 2
  • DOI: 10.1149/1.1531871

Nature of magnetic excitations in superconducting BaFe1.9Ni0.1As2
journal, March 2012

  • Liu, Mengshu; Harriger, Leland W.; Luo, Huiqian
  • Nature Physics, Vol. 8, Issue 5
  • DOI: 10.1038/nphys2268

Doping dependence of spin excitations and its correlations with high-temperature superconductivity in iron pnictides
journal, December 2013

  • Wang, Meng; Zhang, Chenglin; Lu, Xingye
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3874

Preparation of Mn-doped BaTiO3 nanoparticles and their magnetic properties
journal, September 2008

  • Tong, Xiaoran; Lin, Yuan-Hua; Zhang, Songyin
  • Journal of Applied Physics, Vol. 104, Issue 6
  • DOI: 10.1063/1.2973202

Influences of annealing temperature on structural characterization and magnetic properties of Mn-doped BaTiO 3 ceramics
journal, July 2012

  • Phan, The-Long; Zhang, P.; Grinting, D.
  • Journal of Applied Physics, Vol. 112, Issue 1
  • DOI: 10.1063/1.4733691

Evidence for the stabilization of manganese ion as Mn (II) and Mn (IV) in α-Zn2P2O7: Probed by EPR, luminescence and electrochemical studies
journal, May 2014


Theoretical Prediction of Magnetic Properties of Ba(Ti1-xMx)O3 (M=Sc,V,Cr,Mn,Fe,Co,Ni,Cu)
journal, December 2001

  • Nakayama, Hiroyuki; Katayama-Yoshida, Hiroshi
  • Japanese Journal of Applied Physics, Vol. 40, Issue Part 2, No. 12B
  • DOI: 10.1143/JJAP.40.L1355

Structural, optical and magnetic properties of polycrystalline BaTi 1−x Fe x O 3 ceramics
journal, August 2011

  • Dang, N. V.; Thanh, T. D.; Hong, L. V.
  • Journal of Applied Physics, Vol. 110, Issue 4
  • DOI: 10.1063/1.3625235

Structural and optical properties of chromium-doped hexagonal barium titanate ceramics
journal, February 2008


Collapse of magnetic moment drives the Mott transition in MnO
journal, February 2008

  • Kuneš, Jan; Lukoyanov, Alexey V.; Anisimov, Vladimir I.
  • Nature Materials, Vol. 7, Issue 3
  • DOI: 10.1038/nmat2115

A new route to magnetic ferroelectrics: Magnetoelectrics
journal, December 2004

  • Ederer, Claude; Spaldin, Nicola A.
  • Nature Materials, Vol. 3, Issue 12
  • DOI: 10.1038/nmat1265

Rigorous Definition of Oxidation States of Ions in Solids
journal, April 2012


ABINIT: First-principles approach to material and nanosystem properties
journal, December 2009


Electronic structure calculations with dynamical mean-field theory
journal, August 2006


Dynamical mean-field theory within the full-potential methods: Electronic structure of CeIrIn 5 , CeCoIn 5 , and CeRhIn 5
journal, May 2010


Ferroelectric distortions in doped ferroelectrics: BaTiO 3 : M ( M = V Fe)
journal, June 2013


Strong Valence Fluctuation in the Quantum Critical Heavy Fermion Superconductor β YbAlB 4 : A Hard X-Ray Photoemission Study
journal, June 2010


Charge states of ions, and mechanisms of charge ordering transitions
journal, June 2014


How Correlated is the FeSe / SrTiO 3 System?
journal, August 2017


Strong pressure-dependent electron-phonon coupling in FeSe
journal, June 2014


Electronic properties of 3 d transitional metal pnictides: A comparative study by optical spectroscopy
journal, October 2012


Exact Double Counting in Combining the Dynamical Mean Field Theory and the Density Functional Theory
journal, November 2015


Fluctuating valence in a correlated solid and the anomalous properties of δ-plutonium
journal, March 2007


More accurate generalized gradient approximation for solids
journal, June 2006


Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO 3 thin films
journal, April 2011

  • Shuai, Yao; Zhou, Shengqiang; Bürger, Danilo
  • Journal of Applied Physics, Vol. 109, Issue 8
  • DOI: 10.1063/1.3576125

Low-temperature magnetic fluctuations in the Kondo insulator SmB 6
journal, April 2014


Improving the Functional Control of Aged Ferroelectrics Using Insights from Atomistic Modeling
journal, October 2017


Pressure suppression of electron correlation in the collapsed tetragonal phase of CaFe 2 As 2 : A DFT-DMFT investigation
journal, August 2014


Local-density functional and on-site correlations: The electronic structure of La 2 CuO 4 and LaCuO 3
journal, May 1994


Spin fluctuations and frustrated magnetism in multiferroic FeVO 4
journal, May 2014


Kinetic frustration and the nature of the magnetic and paramagnetic states in iron pnictides and iron chalcogenides
journal, September 2011

  • Yin, Z. P.; Haule, K.; Kotliar, G.
  • Nature Materials, Vol. 10, Issue 12
  • DOI: 10.1038/nmat3120

3C–6H phase transition in BaTiO 3 induced by Fe ions: an electron paramagnetic resonance study
journal, November 2008


Evaluation of lattice site and valence of manganese in hexagonal BaTiO 3 by electron paramagnetic resonance
journal, July 2005

  • Böttcher, R.; Langhammer, H. T.; Müller, T.
  • Journal of Physics: Condensed Matter, Vol. 17, Issue 32
  • DOI: 10.1088/0953-8984/17/32/006

Structural phase separation and optical and magnetic properties of BaTi 1−x Mn x O 3 multiferroics
journal, June 2012

  • Dang, N. V.; Phan, The-Long; Thanh, T. D.
  • Journal of Applied Physics, Vol. 111, Issue 11
  • DOI: 10.1063/1.4725195

Effects of manganese addition on the electronic structure of BaTiO 3
journal, June 2015


A ten-year perspective on dilute magnetic semiconductors and oxides
journal, November 2010


Multiscale simulations of defect dipole–enhanced electromechanical coupling at dilute defect concentrations
journal, August 2017

  • Liu, Shi; Cohen, R. E.
  • Applied Physics Letters, Vol. 111, Issue 8
  • DOI: 10.1063/1.4989670

First-principles theory of dilute magnetic semiconductors
journal, May 2010


Symmetry breaking in occupation number based slave-particle methods
journal, October 2017


Electron paramagnetic resonance parameters of Mn4+ ion in h-BaTiO3 crystal from a two-mechanism model
journal, March 2009


Strong Correlations from Hund’s Coupling
journal, April 2013


In situ observation of reversible domain switching in aged Mn-doped BaTiO 3 single crystals
journal, May 2005


Quantum spin fluctuations in the bulk insulating state of pure and Fe-doped SmB 6
journal, June 2017


Evidence for valence fluctuation of Fe in Sr2FeMoO6−w double perovskite
journal, May 2000

  • Lindén, J.; Yamamoto, T.; Karppinen, M.
  • Applied Physics Letters, Vol. 76, Issue 20
  • DOI: 10.1063/1.126518

Effects of electron correlations on transport properties of iron at Earth’s core conditions
journal, January 2015


Simple, Unambiguous Theoretical Approach to Oxidation State Determination via First-Principles Calculations
journal, October 2011

  • Sit, Patrick H. -L.; Car, Roberto; Cohen, Morrel H.
  • Inorganic Chemistry, Vol. 50, Issue 20
  • DOI: 10.1021/ic2013107

Formal Valence, 3 d -Electron Occupation, and Charge-Order Transitions
journal, November 2012