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:
-
[1];
[1];
[2]
- Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
- 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. 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. 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}
}
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