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.
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).
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.
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Accepted/In Press date: 24 September 2018
e-pub ahead of print date: 24 September 2018
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Local EPrints ID: 423512
URI: http://eprints.soton.ac.uk/id/eprint/423512
ISSN: 1433-7851
PURE UUID: bd144b91-b7f0-43bd-954b-161085f49d50
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Date deposited: 25 Sep 2018 16:30
Last modified: 16 Mar 2024 07:06
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Author:
Luc M. LeBlanc
Author:
Stephen G. Dale
Author:
Christopher R. Taylor
Author:
Axel D. Becke
Author:
Erin R. Johnson
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