Multi-phonon proton transfer pathway in a molecular organic ferroelectric crystal

Matthew T.O. Okenyi, Laura E. Ratcliff, Aron Walsh

Research output: Contribution to journalArticlepeer-review

Abstract

While the majority of ferroelectrics research has been focused on inorganic ceramics, molecular ferroelectrics can also combine large spontaneous polarization with high Curie temperatures. However, the microscopic mechanism of their ferroelectric switching is not fully understood. We explore proton tautomerism in the prototypical case of croconic acid, C5O5H2. In order to determine how efficiently ferroelectricity in croconic acid is described in terms of itsΓ-point phonon modes, the minimum energy path between its structural ground states is approximated by projection onto reduced basis sets formed from subsets of these modes. The potential energy curve along the minimum energy path was found to be sensitive to the order of proton transfer, which requires a large subset (8) of the modes to be approximated accurately. Our findings suggest rules for the construction of effective Hamiltonians to describe proton transfer ferroelectrics.

Original languageEnglish
Pages (from-to)2885-2890
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number4
DOIs
Publication statusPublished - 2021 Jan 28

Bibliographical note

Funding Information:
This work was supported through a studentship in the Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London funded by the EPSRC (EP/L015579/1). LER acknowledges support from an EPSRC Early Career Research Fellowship (EP/P033253/1) and the Thomas Young Centre under grant number TYC-101.Viaour membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). We would finally like to thank Karin Rabe for insightful discussions and advice.

Funding Information:
This work was supported through a studentship in the Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London funded by the EPSRC (EP/L015579/1). LER acknowledges support from an EPSRC Early Career Research Fellowship (EP/P033253/1) and the Thomas Young Centre under grant number TYC-101. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac. uk). We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). We would finally like to thank Karin Rabe for insightful discussions and advice.

Publisher Copyright:
© the Owner Societies 2021.

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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