St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  •   St Andrews Research Repository
  • University of St Andrews Research
  • University of St Andrews Research
  • University of St Andrews Research
  • View Item
  • Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Ensemble-based modeling of the NMR spectra of solid solutions : cation disorder in Y2(Sn,Ti)2O7

Thumbnail
View/Open
Moran_2019_Ensemble_based_modelling_JACS_17838.pdf (2.292Mb)
Date
06/11/2019
Author
Moran, Robert F.
McKay, David
Tornstrom, Paulynne
Aziz, Alex
Fernandes, Arantxa
Grau-Crespo, Ricardo
Ashbrook, Sharon E.
Keywords
Site occupancy disorder
Solid-state NMR spectroscopy
Density functional theory
Pyrochlores
QD Chemistry
NDAS
BDC
R2C
Metadata
Show full item record
Abstract
The sensitivity of NMR to the local environment, without the need for any long-range order, makes it an ideal tool for the characterization of disordered materials. Computational prediction of NMR parameters can be of considerable help in the interpretation and assignment of NMR spectra of solids, but the statistical representation of all possible chemical environments for a solid solution is challenging. Here, we illustrate the use of a symmetry-adapted configurational ensemble in the simulation of NMR spectra, in combination with solid-state NMR experiments. We show that for interpretation of the complex and overlapped lineshapes that are typically observed, it is important to go beyond a single-configuration representation or a simple enumeration of local environments. The ensemble method leads to excellent agreement between simulated and experimental spectra for Y2(Sn,Ti)2O7 pyrochlore ceramics, where the overlap of signals from different local environments prevents a simple decomposition of the experimental spectral lineshapes. The inclusion of a Boltzmann weighting confirms that the best agreement with experiment is obtained at higher temperatures, in the limit of full disorder. We also show that to improve agreement with experiment, in particular at low dopant concentrations, larger supercells are needed, which might require alternative simulation approaches as the complexity of the system increases. It is clear that ensemble-based modeling approaches in conjunction with NMR spectroscopy offer great potential for understanding configurational disorder, ultimately aiding the future design of functional materials.
Citation
Moran , R F , McKay , D , Tornstrom , P , Aziz , A , Fernandes , A , Grau-Crespo , R & Ashbrook , S E 2019 , ' Ensemble-based modeling of the NMR spectra of solid solutions : cation disorder in Y 2 (Sn,Ti) 2 O 7 ' , Journal of the American Chemical Society , vol. 141 , no. 44 , pp. 17838-17846 . https://doi.org/10.1021/jacs.9b09036
Publication
Journal of the American Chemical Society
Status
Peer reviewed
DOI
https://doi.org/10.1021/jacs.9b09036
ISSN
0002-7863
Type
Journal article
Rights
Copyright © 2019 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Description
Funding: ERC (EU FP7 Consolidator Grant 614290 ‘‘EXONMR’’). Royal Society and Wolfson Foundation merit award (SEA). We acknowledge support from the Collaborative Computational Project on NMR Crystallography CCP-NC funded by EPSRC (EP/M022501/1) and the UKCP consortium funded by EPSRC (EP/K013564/1). For computational resources we are grateful to the UK Materials and Molecular Modelling Hub, which is partially funded by EPSRC (EP/P020194/1), and to the UK HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202).
Collections
  • University of St Andrews Research
URI
http://hdl.handle.net/10023/19085

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter