Gillet, N;
Berstis, L;
Wu, X;
Gajdos, F;
Heck, A;
de la Lande, A;
Blumberger, J;
(2016)
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.
Journal of Chemical Theory and Computation
, 12
(10)
pp. 4793-4805.
10.1021/acs.jctc.6b00564.
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Abstract
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.
| Type: | Article |
|---|---|
| Title: | 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 |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acs.jctc.6b00564 |
| Publisher version: | http://dx.doi.org/10.1021/acs.jctc.6b00564 |
| Language: | English |
| Additional information: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see: http://dx.doi.org/10.1021/acs.jctc.6b00564. |
| Keywords: | science & technology, physical sciences, chemistry, physical, physics, atomic, molecular & chemical, chemistry, physics, generalized gradient approximation, excitation-energy transfer, transfer matrix-elements, gaussian-basis sets, ab-initio, wave-functions, perturbation-theory, through-bond, organic semiconductors, block diagonalization |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1529295 |
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