Show simple item record Heaton-Burgess, T Yang, W
dc.coverage.spatial United States 2011-04-15T16:46:51Z 2010-06-21
dc.identifier.citation J Chem Phys, 2010, 132 (23), pp. 234113 - ?
dc.description.abstract The ground state structure of C(4N+2) rings is believed to exhibit a geometric transition from angle alternation (N < or = 2) to bond alternation (N > 2). All previous density functional theory (DFT) studies on these molecules have failed to reproduce this behavior by predicting either that the transition occurs at too large a ring size, or that the transition leads to a higher symmetry cumulene. Employing the recently proposed perspective of delocalization error within DFT we rationalize this failure of common density functional approximations (DFAs) and present calculations with the rCAM-B3LYP exchange-correlation functional that show an angle-to-bond-alternation transition between C(10) and C(14). The behavior exemplified here manifests itself more generally as the well known tendency of DFAs to bias toward delocalized electron distributions as favored by Huckel aromaticity, of which the C(4N+2) rings provide a quintessential example. Additional examples are the relative energies of the C(20) bowl, cage, and ring isomers; we show that the results from functionals with minimal delocalization error are in good agreement with CCSD(T) results, in contrast to other commonly used DFAs. An unbiased DFT treatment of electron delocalization is a key for reliable prediction of relative stability and hence the structures of complex molecules where many structure stabilization mechanisms exist.
dc.format.extent 234113 - ?
dc.language eng
dc.language.iso en_US en_US
dc.relation.ispartof J Chem Phys
dc.relation.isversionof 10.1063/1.3445266
dc.title Structural manifestation of the delocalization error of density functional approximations: C(4N+2) rings and C(20) bowl, cage, and ring isomers.
dc.type Journal Article
dc.description.version Version of Record en_US 2010-6-21 en_US
duke.description.endpage 234113 en_US
duke.description.issue 23 en_US
duke.description.startpage 234113 en_US
duke.description.volume 132 en_US
dc.relation.journal Journal of Chemical Physics en_US
pubs.issue 23
pubs.organisational-group /Duke
pubs.organisational-group /Duke/Trinity College of Arts & Sciences
pubs.organisational-group /Duke/Trinity College of Arts & Sciences/Chemistry
pubs.organisational-group /Duke/Trinity College of Arts & Sciences/Physics
pubs.publication-status Published
pubs.volume 132
dc.identifier.eissn 1089-7690

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