Models of Polaron Transport in Inorganic and Hybrid Organic-Inorganic Titanium Oxides

Kazuki Morita; Matthias J. Golomb; Miguel Rivera; Aron Walsh

doi:10.1021/acs.chemmater.3c00322

Models of Polaron Transport in Inorganic and Hybrid Organic-Inorganic Titanium Oxides

Kazuki Morita, Matthias J. Golomb, Miguel Rivera, Aron Walsh

Department of Physics

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Polarons are a type of localized excess charge in materials and often form in transition metal oxides. The large effective mass and confined nature of polarons make them of fundamental interest for photochemical and electrochemical reactions. The most studied polaronic system is rutile TiO₂ where electron addition results in small polaron formation through the reduction of Ti(IV) d⁰ to Ti(III) d¹ centers. Using this model system, we perform a systematic analysis of the potential energy surface based on semiclassical Marcus theory parametrized from the first-principles potential energy landscape. We show that F-doped TiO₂ only binds polaron weakly with effective dielectric screening after the second nearest neighbor. To tailor the polaron transport, we compare TiO₂ to two metal-organic frameworks (MOFs): MIL-125 and ACM-1. The choice of MOF ligands and connectivity of the TiO₆ octahedra largely vary the shape of the diabatic potential energy surface and the polaron mobility. Our models are applicable to other polaronic materials.

Original language	English
Pages (from-to)	3652-3659
Number of pages	8
Journal	Chemistry of Materials
Volume	35
Issue number	9
DOIs	https://doi.org/10.1021/acs.chemmater.3c00322
State	Published - 9 May 2023

Bibliographical note

Funding Information:
Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194 and EP/T022213).

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

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title = "Models of Polaron Transport in Inorganic and Hybrid Organic-Inorganic Titanium Oxides",

abstract = "Polarons are a type of localized excess charge in materials and often form in transition metal oxides. The large effective mass and confined nature of polarons make them of fundamental interest for photochemical and electrochemical reactions. The most studied polaronic system is rutile TiO2 where electron addition results in small polaron formation through the reduction of Ti(IV) d0 to Ti(III) d1 centers. Using this model system, we perform a systematic analysis of the potential energy surface based on semiclassical Marcus theory parametrized from the first-principles potential energy landscape. We show that F-doped TiO2 only binds polaron weakly with effective dielectric screening after the second nearest neighbor. To tailor the polaron transport, we compare TiO2 to two metal-organic frameworks (MOFs): MIL-125 and ACM-1. The choice of MOF ligands and connectivity of the TiO6 octahedra largely vary the shape of the diabatic potential energy surface and the polaron mobility. Our models are applicable to other polaronic materials.",

author = "Kazuki Morita and Golomb, {Matthias J.} and Miguel Rivera and Aron Walsh",

note = "Funding Information: Via our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194 and EP/T022213). Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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AU - Golomb, Matthias J.

AU - Rivera, Miguel

AU - Walsh, Aron

N1 - Funding Information: Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194 and EP/T022213). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

PY - 2023/5/9

Y1 - 2023/5/9

N2 - Polarons are a type of localized excess charge in materials and often form in transition metal oxides. The large effective mass and confined nature of polarons make them of fundamental interest for photochemical and electrochemical reactions. The most studied polaronic system is rutile TiO2 where electron addition results in small polaron formation through the reduction of Ti(IV) d0 to Ti(III) d1 centers. Using this model system, we perform a systematic analysis of the potential energy surface based on semiclassical Marcus theory parametrized from the first-principles potential energy landscape. We show that F-doped TiO2 only binds polaron weakly with effective dielectric screening after the second nearest neighbor. To tailor the polaron transport, we compare TiO2 to two metal-organic frameworks (MOFs): MIL-125 and ACM-1. The choice of MOF ligands and connectivity of the TiO6 octahedra largely vary the shape of the diabatic potential energy surface and the polaron mobility. Our models are applicable to other polaronic materials.

AB - Polarons are a type of localized excess charge in materials and often form in transition metal oxides. The large effective mass and confined nature of polarons make them of fundamental interest for photochemical and electrochemical reactions. The most studied polaronic system is rutile TiO2 where electron addition results in small polaron formation through the reduction of Ti(IV) d0 to Ti(III) d1 centers. Using this model system, we perform a systematic analysis of the potential energy surface based on semiclassical Marcus theory parametrized from the first-principles potential energy landscape. We show that F-doped TiO2 only binds polaron weakly with effective dielectric screening after the second nearest neighbor. To tailor the polaron transport, we compare TiO2 to two metal-organic frameworks (MOFs): MIL-125 and ACM-1. The choice of MOF ligands and connectivity of the TiO6 octahedra largely vary the shape of the diabatic potential energy surface and the polaron mobility. Our models are applicable to other polaronic materials.

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Models of Polaron Transport in Inorganic and Hybrid Organic-Inorganic Titanium Oxides

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