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 Brédas

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124 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-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.

Original languageEnglish (US)
Pages (from-to)602-609
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume7
Issue number3
DOIs
StatePublished - Mar 8 2011
Externally publishedYes

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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