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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

In this paper, 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 p-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 exponentialmore » decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, 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.« less
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [3] ;  [4] ;  [1]
  1. Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Physical Chemistry
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
  3. Univ. Paris-Sud, Orsay (France). Laboratoire de Chimie-Physique; Univ. Paris-Saclay, Orsay (France); Centre National de la Recherche Scientifique (CNRS), Orsay (France)
  4. Univ. College London (United Kingdom). Dept. of Physics and Astronomy
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1549-9618
Grant/Contract Number:
AC36-08GO28308; EP/L000202
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 1549-9618
American Chemical Society
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); Alexander von Humboldt foundation
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transfer integrals; electron transfer; density functional theory