Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case
KAUST Grant NumberKUS-C1-015-21
Online Publication Date2011-01-18
Print Publication Date2011-03-08
Permanent link to this recordhttp://hdl.handle.net/10754/598242
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AbstractWe have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMO TTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined. © 2011 American Chemical Society.
CitationSini G, Sears JS, Brédas J-L (2011) Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case. Journal of Chemical Theory and Computation 7: 602–609. Available: http://dx.doi.org/10.1021/ct1005517.
SponsorsThis work has been supported by the Center for Advanced Molecular Photovoltaics, Award No. KUS-C1-015-21, made by King Abdullah University of Science and Technology (KAUST); the Georgia Research Alliance; the STC Program of the National Science Foundation under Award DMR-0120967; and the University of Cergy-Pontoise, France.
PublisherAmerican Chemical Society (ACS)