Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction

dc.contributorAalto-yliopistofi
dc.contributorAalto Universityen
dc.contributor.authorCheng, Xinxin
dc.contributor.authorZhang, Yao
dc.contributor.authorJónsson, Elvar
dc.contributor.authorJónsson, Hannes
dc.contributor.authorWeber, Peter M.
dc.contributor.departmentBrown University
dc.contributor.departmentDepartment of Applied Physics
dc.date.accessioned2017-04-20T10:12:47Z
dc.date.available2017-04-20T10:12:47Z
dc.date.issued2016-03-16
dc.description.abstractDensity 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.en
dc.description.versionPeer revieweden
dc.format.extent1-6
dc.format.mimetypeapplication/pdf
dc.identifier.citationCheng , X , Zhang , Y , Jónsson , E , Jónsson , H & Weber , P M 2016 , ' Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction ' , Nature Communications , vol. 7 , 11013 , pp. 1-6 . https://doi.org/10.1038/ncomms11013en
dc.identifier.doi10.1038/ncomms11013
dc.identifier.issn2041-1723
dc.identifier.otherPURE UUID: 0ca44dfe-3ae1-4672-93ae-1c6355135611
dc.identifier.otherPURE ITEMURL: https://research.aalto.fi/en/publications/0ca44dfe-3ae1-4672-93ae-1c6355135611
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dc.identifier.otherPURE FILEURL: https://research.aalto.fi/files/11503328/ncomms11013.pdf
dc.identifier.urihttps://aaltodoc.aalto.fi/handle/123456789/25193
dc.identifier.urnURN:NBN:fi:aalto-201704203623
dc.language.isoenen
dc.relation.ispartofseriesNATURE COMMUNICATIONSen
dc.relation.ispartofseriesVolume 7en
dc.rightsopenAccessen
dc.titleCharge localization in a diamine cation provides a test of energy functionals and self-interaction correctionen
dc.typeA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessäfi
dc.type.versionpublishedVersion
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