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Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction
Density functional theory (DFT) is widely applied in calculations of molecules and materials. Yet, it suffers from a well-known over-emphasis on charge delocalization arising from self-interaction error that destabilizes localized states. Here, using the symmetric diamine N,N′-dimethylpiperazine as...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4799366/ https://www.ncbi.nlm.nih.gov/pubmed/26980327 http://dx.doi.org/10.1038/ncomms11013 |
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author | Cheng, Xinxin Zhang, Yao Jónsson, Elvar Jónsson, Hannes Weber, Peter M. |
author_facet | Cheng, Xinxin Zhang, Yao Jónsson, Elvar Jónsson, Hannes Weber, Peter M. |
author_sort | Cheng, Xinxin |
collection | PubMed |
description | Density functional theory (DFT) is widely applied in calculations of molecules and materials. Yet, it suffers from a well-known over-emphasis on charge delocalization arising from self-interaction error that destabilizes localized states. Here, using the symmetric diamine N,N′-dimethylpiperazine as a model, we have experimentally determined the relative energy of a state with positive charge localized on one of the two nitrogen atoms, and a state with positive charge delocalized over both nitrogen atoms. The charge-localized state was found to be 0.33 (0.04) eV higher in energy than the charge-delocalized state. This provides an important test of theoretical approaches to electronic structure calculations. Calculations with all DFT functionals commonly used today, including hybrid functionals with exact exchange, fail to predict a stable charge-localized state. However, the application of an explicit self-interaction correction to a semi-local functional identifies both states and gives relative energy in excellent agreement with both experiment and CCSD(T) calculations. |
format | Online Article Text |
id | pubmed-4799366 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Nature Publishing Group |
record_format | MEDLINE/PubMed |
spelling | pubmed-47993662016-03-23 Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction Cheng, Xinxin Zhang, Yao Jónsson, Elvar Jónsson, Hannes Weber, Peter M. Nat Commun Article Density functional theory (DFT) is widely applied in calculations of molecules and materials. Yet, it suffers from a well-known over-emphasis on charge delocalization arising from self-interaction error that destabilizes localized states. Here, using the symmetric diamine N,N′-dimethylpiperazine as a model, we have experimentally determined the relative energy of a state with positive charge localized on one of the two nitrogen atoms, and a state with positive charge delocalized over both nitrogen atoms. The charge-localized state was found to be 0.33 (0.04) eV higher in energy than the charge-delocalized state. This provides an important test of theoretical approaches to electronic structure calculations. Calculations with all DFT functionals commonly used today, including hybrid functionals with exact exchange, fail to predict a stable charge-localized state. However, the application of an explicit self-interaction correction to a semi-local functional identifies both states and gives relative energy in excellent agreement with both experiment and CCSD(T) calculations. Nature Publishing Group 2016-03-16 /pmc/articles/PMC4799366/ /pubmed/26980327 http://dx.doi.org/10.1038/ncomms11013 Text en Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Article Cheng, Xinxin Zhang, Yao Jónsson, Elvar Jónsson, Hannes Weber, Peter M. Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title | Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title_full | Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title_fullStr | Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title_full_unstemmed | Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title_short | Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
title_sort | charge localization in a diamine cation provides a test of energy functionals and self-interaction correction |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4799366/ https://www.ncbi.nlm.nih.gov/pubmed/26980327 http://dx.doi.org/10.1038/ncomms11013 |
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