The University of Southampton
University of Southampton Institutional Repository
Warning ePrints Soton is experiencing an issue with some file downloads not being available. We are working hard to fix this. Please bear with us.

Pervasive delocalisation error causes spurious proton transfer in organic acid-base co-crystals

Pervasive delocalisation error causes spurious proton transfer in organic acid-base co-crystals
Pervasive delocalisation error causes spurious proton transfer in organic acid-base co-crystals
Dispersion-corrected density-functional theory (DFT-D) methods have become the workhorse of many computational protocols for molecular crystal structure prediction due to their efficiency and convenience. However, certain limitations of DFT, such as delocalisation error, are often overlooked or are too expensive to remedy in solid-state applications. This error can lead to artificial stabilisation of charge-transfer and, in this work, it is found to affect the correct identification of the protonation site in multicomponent acid-base crystals. As such, commonly used DFT-D methods cannot be applied with any reliability to the study of acid-base co-crystals or salts, while hybrid functionals remain too restrictive for routine use. This presents an impetus for the development of new functionals with reduced delocalisation error for solid-state applications; the structures studied herein constitute an excellent benchmark for this purpose.
1433-7851
LeBlanc, Luc M.
17817be6-5ae8-4226-a5c7-afce1e2b8545
Dale, Stephen G.
8302d5ed-3395-4d74-93e5-5ca3e1ee280d
Taylor, Christopher R.
95bebf3a-a98a-453c-acb6-aebc451bd5a8
Becke, Axel D.
52b64c18-ffaa-477d-8538-fade9d5475c2
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Johnson, Erin R.
b87e2b47-e33f-41ff-a2f1-a79c41a47fba
LeBlanc, Luc M.
17817be6-5ae8-4226-a5c7-afce1e2b8545
Dale, Stephen G.
8302d5ed-3395-4d74-93e5-5ca3e1ee280d
Taylor, Christopher R.
95bebf3a-a98a-453c-acb6-aebc451bd5a8
Becke, Axel D.
52b64c18-ffaa-477d-8538-fade9d5475c2
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Johnson, Erin R.
b87e2b47-e33f-41ff-a2f1-a79c41a47fba

LeBlanc, Luc M., Dale, Stephen G., Taylor, Christopher R., Becke, Axel D., Day, Graeme M. and Johnson, Erin R. (2018) Pervasive delocalisation error causes spurious proton transfer in organic acid-base co-crystals. Angewandte Chemie International Edition. (doi:10.1002/anie.201809381).

Record type: Article

Abstract

Dispersion-corrected density-functional theory (DFT-D) methods have become the workhorse of many computational protocols for molecular crystal structure prediction due to their efficiency and convenience. However, certain limitations of DFT, such as delocalisation error, are often overlooked or are too expensive to remedy in solid-state applications. This error can lead to artificial stabilisation of charge-transfer and, in this work, it is found to affect the correct identification of the protonation site in multicomponent acid-base crystals. As such, commonly used DFT-D methods cannot be applied with any reliability to the study of acid-base co-crystals or salts, while hybrid functionals remain too restrictive for routine use. This presents an impetus for the development of new functionals with reduced delocalisation error for solid-state applications; the structures studied herein constitute an excellent benchmark for this purpose.

Text
accepted manuscript - Accepted Manuscript
Download (1MB)
Text
supplementary information file
Restricted to Repository staff only
Request a copy

More information

Accepted/In Press date: 24 September 2018
e-pub ahead of print date: 24 September 2018

Identifiers

Local EPrints ID: 423512
URI: http://eprints.soton.ac.uk/id/eprint/423512
ISSN: 1433-7851
PURE UUID: bd144b91-b7f0-43bd-954b-161085f49d50
ORCID for Christopher R. Taylor: ORCID iD orcid.org/0000-0001-9465-5742
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 25 Sep 2018 16:30
Last modified: 26 Nov 2021 07:10

Export record

Altmetrics

Contributors

Author: Luc M. LeBlanc
Author: Stephen G. Dale
Author: Christopher R. Taylor ORCID iD
Author: Axel D. Becke
Author: Graeme M. Day ORCID iD
Author: Erin R. Johnson

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×