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Title: Polaronic structure of excess electrons and holes for a series of bulk iron oxides

Abstract

Iron oxides such as hematite (α-Fe2O3) play an important role in diverse fields ranging from biogeochemistry to photocatalysis. Here we perform calculations of both the electron and electron hole polaron structures and associated reorganisation energies for a series of bulk iron oxides: hematite (α-Fe2O3), lepidocrocite (γ-FeOOH), goethite (α-FeOOH) and white rust (Fe(OH)2). Through the use of gap-optimized hybrid functionals and large supercells under periodic boundary conditions, we remove some of the complications and uncertainties present in earlier cluster model calculations. It is found that while the electron hole polaron in these materials generally localises onto a single iron site, the electron polaron localises across two iron sites of the same spin layer as a consequence of the lower reorganisation energy for electrons compared to holes. An exception to these trends is the hole of goethite, which according to our calculations does not form a localised polaron.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
  2. Pacific Northwest National Laboratory, Richland, USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1601323
Alternate Identifier(s):
OSTI ID: 1638965
Report Number(s):
PNNL-SA-151330
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC05-76RL01830; EP/L000202; EP/R029431; EP/P020194
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Volume: 22 Journal Issue: 19; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ahart, Christian S., Blumberger, Jochen, and Rosso, Kevin M. Polaronic structure of excess electrons and holes for a series of bulk iron oxides. United Kingdom: N. p., 2020. Web. doi:10.1039/C9CP06482F.
Ahart, Christian S., Blumberger, Jochen, & Rosso, Kevin M. Polaronic structure of excess electrons and holes for a series of bulk iron oxides. United Kingdom. doi:https://doi.org/10.1039/C9CP06482F
Ahart, Christian S., Blumberger, Jochen, and Rosso, Kevin M. Wed . "Polaronic structure of excess electrons and holes for a series of bulk iron oxides". United Kingdom. doi:https://doi.org/10.1039/C9CP06482F.
@article{osti_1601323,
title = {Polaronic structure of excess electrons and holes for a series of bulk iron oxides},
author = {Ahart, Christian S. and Blumberger, Jochen and Rosso, Kevin M.},
abstractNote = {Iron oxides such as hematite (α-Fe2O3) play an important role in diverse fields ranging from biogeochemistry to photocatalysis. Here we perform calculations of both the electron and electron hole polaron structures and associated reorganisation energies for a series of bulk iron oxides: hematite (α-Fe2O3), lepidocrocite (γ-FeOOH), goethite (α-FeOOH) and white rust (Fe(OH)2). Through the use of gap-optimized hybrid functionals and large supercells under periodic boundary conditions, we remove some of the complications and uncertainties present in earlier cluster model calculations. It is found that while the electron hole polaron in these materials generally localises onto a single iron site, the electron polaron localises across two iron sites of the same spin layer as a consequence of the lower reorganisation energy for electrons compared to holes. An exception to these trends is the hole of goethite, which according to our calculations does not form a localised polaron.},
doi = {10.1039/C9CP06482F},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 19,
volume = 22,
place = {United Kingdom},
year = {2020},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
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DOI: https://doi.org/10.1039/C9CP06482F

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Works referenced in this record:

LDA + U and GGA + U studies of Al-rich and bulk goethite (α-FeOOH)
journal, January 2013


Charge transport in metal oxides: A theoretical study of hematite α-Fe2O3
journal, April 2005

  • Iordanova, N.; Dupuis, M.; Rosso, K. M.
  • The Journal of Chemical Physics, Vol. 122, Issue 14
  • DOI: 10.1063/1.1869492

Electron transport in pure and substituted iron oxyhydroxides by small-polaron migration
journal, June 2014

  • Alexandrov, Vitaly; Rosso, Kevin M.
  • The Journal of Chemical Physics, Vol. 140, Issue 23
  • DOI: 10.1063/1.4882065

Corresponding Orbitals Derived from Periodic Bloch States for Electron Transfer Calculations of Transition Metal Oxides
journal, June 2018

  • Bylaska, Eric J.; Rosso, Kevin
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 8
  • DOI: 10.1021/acs.jctc.7b01180

Kinetic Monte Carlo model of charge transport in hematite (α-Fe2O3)
journal, September 2007

  • Kerisit, Sebastien; Rosso, Kevin M.
  • The Journal of Chemical Physics, Vol. 127, Issue 12
  • DOI: 10.1063/1.2768522

An ab initio model of electron transport in hematite (α-Fe2O3) basal planes
journal, April 2003

  • Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel
  • The Journal of Chemical Physics, Vol. 118, Issue 14, p. 6455-6466
  • DOI: 10.1063/1.1558534

Energy Levels and Redox Properties of Aqueous Mn 2+/3+ from Photoemission Spectroscopy and Density Functional Molecular Dynamics Simulation
journal, July 2010

  • Moens, Jan; Seidel, Robert; Geerlings, Paul
  • The Journal of Physical Chemistry B, Vol. 114, Issue 28
  • DOI: 10.1021/jp101527v

Weak hydrogen bonds in solid hydroxides and hydrates
journal, June 1994


Neutron Diffraction Studies of α-FeOOH
journal, January 1968

  • Szytuła, A.; Burewicz, A.; Dimitrijević, Ž.
  • Physica Status Solidi (b), Vol. 26, Issue 2
  • DOI: 10.1002/pssb.19680260205

Ab initio modeling of Fe( ii ) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces
journal, January 2015

  • Alexandrov, Vitaly; Rosso, Kevin M.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 22
  • DOI: 10.1039/C5CP00921A

The electrical properties of alpha ferric oxide—II.
journal, October 1963

  • Gardner, R. F. G.; Sweett, F.; Tanner, D. W.
  • Journal of Physics and Chemistry of Solids, Vol. 24, Issue 10
  • DOI: 10.1016/0022-3697(63)90235-X

Deviations from piecewise linearity in the solid-state limit with approximate density functionals
journal, January 2015

  • Vlček, Vojtěch; Eisenberg, Helen R.; Steinle-Neumann, Gerd
  • The Journal of Chemical Physics, Vol. 142, Issue 3
  • DOI: 10.1063/1.4905236

Crossover from incoherent to coherent electron tunneling between defects in MgO
journal, December 2012


Density functional theory based calculation of small-polaron mobility in hematite
journal, June 2014


Hydrogen Bonds of gamma-FeOOH.
journal, January 1978


Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide Nanoparticles
journal, September 2012


Constraints to the flat band potential of hematite photo-electrodes
journal, January 2014

  • Hankin, A.; Alexander, J. C.; Kelsall, G. H.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 30
  • DOI: 10.1039/C4CP00096J

First-Principles Modeling of Polaron Formation in TiO 2 Polymorphs
journal, May 2018

  • Elmaslmane, A. R.; Watkins, M. B.; McKenna, K. P.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 7
  • DOI: 10.1021/acs.jctc.8b00199

Proton transfer in the hydrogen-bonded chains of lepidocrocite: a computational study
journal, January 2011

  • Guo, Haibo; Barnard, Amanda S.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 39
  • DOI: 10.1039/c1cp22508a

Hybrid density functional theory band structure engineering in hematite
journal, June 2011

  • Pozun, Zachary D.; Henkelman, Graeme
  • The Journal of Chemical Physics, Vol. 134, Issue 22
  • DOI: 10.1063/1.3598947

The Iron Oxides
book, July 2003


Iron Dissolution from Goethite (α-FeOOH) Surfaces in Water by Ab Initio Enhanced Free-Energy Simulations
journal, June 2018

  • Klyukin, Konstantin; Rosso, Kevin M.; Alexandrov, Vitaly
  • The Journal of Physical Chemistry C, Vol. 122, Issue 28
  • DOI: 10.1021/acs.jpcc.8b03743

Charge transport in micas: The kinetics of FeII/III electron transfer in the octahedral sheet
journal, November 2003

  • Rosso, Kevin M.; Ilton, Eugene S.
  • The Journal of Chemical Physics, Vol. 119, Issue 17
  • DOI: 10.1063/1.1612912

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Structure and Charge Hopping Dynamics in Green Rust
journal, August 2007

  • Wander, Matthew C. F.; Rosso, Kevin M.; Schoonen, Martin A. A.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 30
  • DOI: 10.1021/jp072762n

Constrained density functional theory applied to electron tunnelling between defects in MgO
journal, January 2013

  • Blumberger, Jochen; McKenna, Keith P.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 6
  • DOI: 10.1039/c2cp42537h

The absolute energy positions of conduction and valence bands of selected semiconducting minerals
journal, March 2000

  • Xu, Yong; Schoonen, Martin A. A.
  • American Mineralogist, Vol. 85, Issue 3-4
  • DOI: 10.2138/am-2000-0416

Crystal structure of lepidocrocite FeO(OH) from the electron-diffractometry data
journal, September 2001

  • Zhukhlistov, A. P.
  • Crystallography Reports, Vol. 46, Issue 5
  • DOI: 10.1134/1.1405857

The electrical properties of alpha ferric oxide—I.
journal, October 1963

  • Gardner, R. F. G.; Sweett, F.; Tanner, D. W.
  • Journal of Physics and Chemistry of Solids, Vol. 24, Issue 10
  • DOI: 10.1016/0022-3697(63)90234-8

Benchmark tests of a strongly constrained semilocal functional with a long-range dispersion correction
journal, September 2016


Neutron diffraction studies on the (1−x) Fe2O3 − xRh2O3 system
journal, October 1965


Bonded-atom fragments for describing molecular charge densities
journal, January 1977


Dielectric polarizabilities of ions in oxides and fluorides
journal, January 1993

  • Shannon, R. D.
  • Journal of Applied Physics, Vol. 73, Issue 1
  • DOI: 10.1063/1.353856

Direct Observation of Two Electron Holes in a Hematite Photoanode during Photoelectrochemical Water Splitting
journal, August 2012

  • Braun, Artur; Sivula, Kevin; Bora, Debajeet K.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 32
  • DOI: 10.1021/jp304254k

Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes
journal, March 2011

  • Sivula, Kevin; Le Formal, Florian; Grätzel, Michael
  • ChemSusChem, Vol. 4, Issue 4
  • DOI: 10.1002/cssc.201000416

Hole transport in pure and doped hematite
journal, July 2012

  • Liao, Peilin; Carter, Emily A.
  • Journal of Applied Physics, Vol. 112, Issue 1
  • DOI: 10.1063/1.4730634

A Classical Point Charge Model Study of System Size Dependence of Oxidation and Reorganization Free Energies in Aqueous Solution
journal, January 2008

  • Ayala, Regla; Sprik, Michiel
  • The Journal of Physical Chemistry B, Vol. 112, Issue 2
  • DOI: 10.1021/jp0748516

Infrared lattice vibrations and dielectric dispersion in α Fe 2 O 3
journal, August 1977


Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Synchrotron X-ray study of the electron density in α-Fe 2 O 3
journal, August 1994

  • Maslen, E. N.; Streltsov, V. A.; Streltsova, N. R.
  • Acta Crystallographica Section B Structural Science, Vol. 50, Issue 4
  • DOI: 10.1107/S0108768194002284

Single-Ion Reorganization Free Energy of Aqueous Ru(bpy) 3 2+/3+ and Ru(H 2 O) 6 2+/3+ from Photoemission Spectroscopy and Density Functional Molecular Dynamics Simulation
journal, November 2009

  • Seidel, Robert; Faubel, Manfred; Winter, Bernd
  • Journal of the American Chemical Society, Vol. 131, Issue 44
  • DOI: 10.1021/ja9047834

Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy
journal, September 2019

  • Biswas, Somnath; Wallentine, Spencer; Bandaranayake, Savini
  • The Journal of Chemical Physics, Vol. 151, Issue 10
  • DOI: 10.1063/1.5115163

Density-functional energy gaps of solids demystified
journal, June 2018


Semiconductor-based photocatalysts and photoelectrochemical cells for solar fuel generation: a review
journal, January 2015

  • Li, Jiangtian; Wu, Nianqiang
  • Catalysis Science & Technology, Vol. 5, Issue 3
  • DOI: 10.1039/C4CY00974F

Neutron Diffraction Study of γ-FeOOH
journal, January 1970


Separable dual-space Gaussian pseudopotentials
journal, July 1996


Vibrational spectroscopy of Fe ( OH ) 2 at high pressure: Behavior of the O-H bond
journal, May 2005


Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory
journal, January 2012

  • Valdés, Álvaro; Brillet, Jeremie; Grätzel, Michael
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 1
  • DOI: 10.1039/C1CP23212F

Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface
journal, March 2016

  • von Rudorff, Guido Falk; Jakobsen, Rasmus; Rosso, Kevin M.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
  • DOI: 10.1021/acs.jpclett.6b00165

Auxiliary Density Matrix Methods for Hartree−Fock Exchange Calculations
journal, July 2010

  • Guidon, Manuel; Hutter, Jürg; VandeVondele, Joost
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 8
  • DOI: 10.1021/ct1002225

Improved description of hematite surfaces by the SCAN functional
journal, January 2020

  • Si, Yitao; Li, Mingtao; Zhou, Zhaohui
  • The Journal of Chemical Physics, Vol. 152, Issue 2
  • DOI: 10.1063/1.5134951

Molecular Theories and Simulation of Ions and Polar Molecules in Water
journal, October 1998

  • Hummer, Gerhard; Pratt, Lawrence R.; García, Angel E.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 41
  • DOI: 10.1021/jp982195r

Acidity Constants of the Hematite–Liquid Water Interface from Ab Initio Molecular Dynamics
journal, September 2018

  • Gittus, Oliver R.; von Rudorff, Guido Falk; Rosso, Kevin M.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
  • DOI: 10.1021/acs.jpclett.8b01870

The nuclear and magnetic structure of “white rust”—Fe(OH 0.86 D 0.14 ) 2
journal, January 2000

  • Parise, John B.; Marshall, William G.; Smith, Ronald I.
  • American Mineralogist, Vol. 85, Issue 1
  • DOI: 10.2138/am-2000-0118

Surface simulation studies of the hydration of white rust Fe(OH)2, goethite α-FeO(OH) and hematite α-Fe2O3
journal, April 2007


Reorganization energy associated with small polaron mobility in iron oxide
journal, April 2004

  • Rosso, Kevin M.; Dupuis, Michel
  • The Journal of Chemical Physics, Vol. 120, Issue 15
  • DOI: 10.1063/1.1676117

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations
journal, February 1987

  • Nelsen, Stephen F.; Blackstock, Silas C.; Kim, Yaesil
  • Journal of the American Chemical Society, Vol. 109, Issue 3
  • DOI: 10.1021/ja00237a007

Confronting surface hopping molecular dynamics with Marcus theory for a molecular donor–acceptor system
journal, January 2016

  • Spencer, Jacob; Scalfi, Laura; Carof, Antoine
  • Faraday Discussions, Vol. 195
  • DOI: 10.1039/C6FD00107F

Excitation Gaps of Finite-Sized Systems from Optimally Tuned Range-Separated Hybrid Functionals
journal, April 2012

  • Kronik, Leeor; Stein, Tamar; Refaely-Abramson, Sivan
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 5
  • DOI: 10.1021/ct2009363

Thermodynamics of native point defects in α-Fe2O3: an ab initio study
journal, January 2013

  • Lee, Joohee; Han, Seungwu
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 43
  • DOI: 10.1039/c3cp53311e

Electron Transport in Pure and Doped Hematite
journal, April 2011

  • Liao, Peilin; Toroker, Maytal Caspary; Carter, Emily A.
  • Nano Letters, Vol. 11, Issue 4, p. 1775-1781
  • DOI: 10.1021/nl200356n

Valence Photoemission Spectra of Aqueous Fe 2+/3+ and [Fe(CN) 6 ] 4–/3– and Their Interpretation by DFT Calculations
journal, October 2011

  • Seidel, Robert; Thürmer, Stephan; Moens, Jan
  • The Journal of Physical Chemistry B, Vol. 115, Issue 40
  • DOI: 10.1021/jp203997p