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

Handle URI:
http://hdl.handle.net/10754/598242
Title:
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
Authors:
Sini, Gjergji; Sears, John S.; Brédas, Jean-Luc
Abstract:
We 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.
Citation:
Sini 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.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of Chemical Theory and Computation
KAUST Grant Number:
KUS-C1-015-21
Issue Date:
8-Mar-2011
DOI:
10.1021/ct1005517
PubMed ID:
26596294
Type:
Article
ISSN:
1549-9618; 1549-9626
Sponsors:
This 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.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorSini, Gjergjien
dc.contributor.authorSears, John S.en
dc.contributor.authorBrédas, Jean-Lucen
dc.date.accessioned2016-02-25T13:17:15Zen
dc.date.available2016-02-25T13:17:15Zen
dc.date.issued2011-03-08en
dc.identifier.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.en
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.pmid26596294en
dc.identifier.doi10.1021/ct1005517en
dc.identifier.urihttp://hdl.handle.net/10754/598242en
dc.description.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.en
dc.description.sponsorshipThis 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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleEvaluating 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 Caseen
dc.typeArticleen
dc.identifier.journalJournal of Chemical Theory and Computationen
dc.contributor.institutionGeorgia Institute of Technology, Atlanta, United Statesen
kaust.grant.numberKUS-C1-015-21en
kaust.grant.fundedcenterCenter for Advanced Molecular Photovoltaics (CAMP)en
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