TITLE

Excitonic effects in a time-dependent density functional theory

AUTHOR(S)
Igumenshchev, Kirill I.; Tretiak, Sergei; Chernyak, Vladimir Y.
PUB. DATE
September 2007
SOURCE
Journal of Chemical Physics;9/21/2007, Vol. 127 Issue 11, p114902
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Excited state properties of one-dimensional molecular materials are dominated by many-body interactions resulting in strongly bound confined excitons. These effects cannot be neglected or treated as a small perturbation and should be appropriately accounted for by electronic structure methodologies. We use adiabatic time-dependent density functional theory to investigate the electronic structure of one-dimensional organic semiconductors, conjugated polymers. Various commonly used functionals are applied to calculate the lowest singlet and triplet state energies and oscillator strengths of the poly(phenylenevinylene) and ladder-type (poly)(para-phenylene) oligomers. Local density approximations and gradient-corrected functionals cannot describe bound excitonic states due to lack of an effective attractive Coulomb interaction between photoexcited electrons and holes. In contrast, hybrid density functionals, which include long-range nonlocal and nonadiabatic corrections in a form of a fraction of Hartree-Fock exchange, are able to reproduce the excitonic effects. The resulting finite exciton sizes are strongly dependent on the amount of the orbital exchange included in the functional.
ACCESSION #
26773840

 

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