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

Gjergji Sini; John S. Sears; Jean-Luc Bredas

doi:10.1021/ct1005517

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

Gjergji Sini, John S. Sears, Jean-Luc Bredas^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

137 Scopus citations

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-LUMO_TCNQ 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.

Original language	English (US)
Pages (from-to)	602-609
Number of pages	8
Journal	JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume	7
Issue number	3
DOIs	https://doi.org/10.1021/ct1005517
State	Published - Mar 8 2011
Externally published	Yes

ASJC Scopus subject areas

Computer Science Applications
Physical and Theoretical Chemistry

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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",

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.",

author = "Gjergji Sini and Sears, {John S.} and Jean-Luc Bredas",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2011",

month = mar,

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doi = "10.1021/ct1005517",

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volume = "7",

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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. / Sini, Gjergji; Sears, John S.; Bredas, Jean-Luc.
In: JOURNAL OF CHEMICAL THEORY AND COMPUTATION, Vol. 7, No. 3, 08.03.2011, p. 602-609.

Research output: Contribution to journal › Article › peer-review

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N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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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

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