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Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Chem. Theory Comput. 2016, 12, 10, 4793-4805
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    Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level
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    † Institute of Physical Chemistry, Karlsruhe Institute of Technology, Kaiserstrasse 12, 76131 Karlsruhe, Germany
    ‡ National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
    § Laboratoire de Chimie-Physique, Université Paris Sud, CNRS, Université Paris Saclay, Campus d’Orsay. 15, avenue Jean Perrin, 91405 Cedex Orsay, France
    ⊥ Department of Physics and Astronomy, University College London, Gower Street, London WCIE 6BT, United Kingdom
    *E-mail: [email protected] (L. Berstis).
    *E-mail: [email protected] (A. de la Lande).
    *E-mail: [email protected] (J. Blumberger).
    *E-mail: [email protected] (M. Elstner).
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2016, 12, 10, 4793–4805
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    https://doi.org/10.1021/acs.jctc.6b00564
    Published September 9, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green’s function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor–acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor–acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

    Copyright © 2016 American Chemical Society

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    • Optimized geometries of the different molecules used for TDA calculation; detailed results of functionals, basis, and constraint comparisons (PDF)

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    This article is cited by 47 publications.

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    Cite this: J. Chem. Theory Comput. 2016, 12, 10, 4793–4805
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.6b00564
    Published September 9, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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