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dc.contributor.authorCohen, Aronen
dc.contributor.authorMori-Sánchez, Paulaen
dc.date.accessioned2014-01-29T11:18:58Z
dc.date.available2014-01-29T11:18:58Z
dc.date.issued2014-01-28en
dc.identifier.citationJ. Chem. Phys. 140, 044110 (2014); DOI: http://dx.doi.org/10.1063/1.4858461en
dc.identifier.issn0021-9606
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/245127
dc.description.abstractDiscontinuous changes in the electronic structure upon infinitesimal changes to the Hamiltonian are demonstrated. These are revealed in one and two electron molecular systems by full configuration interaction (FCI) calculations when the realm of the nuclear charge is extended to be fractional. FCI electron densities in these systems show dramatic changes in real space and illustrate the transfer, hopping, and removal of electrons. This is due to the particle nature of electrons seen in stretched systems and is a manifestation of an energy derivative discontinuity at constant number of electrons. Dramatic errors of density functional theory densities are seen in real space as this physics is missing from currently used approximations. The movements of electrons in these simple systems encapsulate those in real physical processes, from chemical reactions to electron transport and pose a great challenge for the development of new electronic structure methods.
dc.description.sponsorshipWe thank the Royal Society and Ramón y Cajal for funding. P.M.S. also acknowledges Grant No. FIS2009-12721 from the Spanish Ministry of Science and Innovation.
dc.languageEnglishen
dc.language.isoenen
dc.publisherAIP Publishing
dc.titleDramatic changes in electronic structure revealed by fractionally charged nucleien
dc.typeArticle
dc.description.versionThis article appeared in the Journal of Chemical Physics 140 and may be found at http://scitation.aip.org/content/aip/journal/jcp/140/4/10.1063/1.4858461.Copyright 2014 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.en
prism.publicationDate2014en
prism.publicationNameJournal of Chemical Physicsen
prism.volume140en
rioxxterms.versionofrecord10.1063/1.4858461en
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2014-01-28en
dc.identifier.eissn1089-7690
rioxxterms.typeJournal Article/Reviewen


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