Modeling noncovalent radical-molecule interactions using conventional density-functional theory: Beware erroneous charge transfer

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DOIResolve DOI: http://doi.org/10.1021/jp3084309
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TypeArticle
Journal titleThe Journal of Physical Chemistry A
ISSN1089-5639
Volume117
Issue5
Pages947952; # of pages: 6
SubjectCoulombic attractions; DFT method; Donor-acceptor complex; Fractional charges; Hartree-Fock exchanges; Highest occupied molecular orbital; Noncovalent; Charge transfer; Density functional theory; Molecular orbitals; Molecules
AbstractConventional density-functional theory (DFT) has the potential to overbind radical-molecule complexes because of erroneous charge transfer. We examined this behavior by exploring the ability of various DFT approximations to predict fractional charge transfer and by quantifying the overbinding in a series of complexes. It is demonstrated that too much charge is transferred from molecules to radicals when the radical singly unoccupied molecular orbitals are predicted to be erroneously too low in energy relative to the molecule highest occupied molecular orbitals, leading to excessive Coulombic attraction. In this respect, DFT methods formulated with little or no Hartree-Fock exchange perform most poorly. The present results illustrate that the charge-transfer problem is much broader than may have been previously expected and is not limited to conventional (i.e., molecule-molecule) donor-acceptor complexes. © 2013 American Chemical Society.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC); National Institute for Nanotechnology (NINT-INNT)
Peer reviewedYes
NPARC number21269850
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Record identifier87f40a51-7a0e-45b1-9ab8-3c61a7dc4e3e
Record created2013-12-13
Record modified2017-03-23
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