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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

Journal Article · · Journal of Chemical Theory and Computation
 [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
+ Show Author Affiliations

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 exponential 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.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); Alexander von Humboldt foundation
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1329526
Report Number(s):
NREL/JA-2700-67308
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 10 Vol. 12; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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  • Valeev, Edward F.; Coropceanu, Veaceslav; da Silva Filho, Demetrio A.
  • Journal of the American Chemical Society, Vol. 128, Issue 30 https://doi.org/10.1021/ja061827h
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Charge Transfer Database for Bio-molecule Tight Binding Model Derived from Thousands of Proteins text January 2018
Multiscale modeling of enzymes: QM-cluster, QM/MM, and QM/MM/MD: A tutorial review journal January 2018
Electron transfer characteristics of 2′-deoxy-2′-fluoro-arabinonucleic acid, a nucleic acid with enhanced chemical stability journal January 2018
Biological relevance of charge transfer branching pathways in photolyases journal January 2019
Computational construction of the electronic Hamiltonian for photoinduced electron transfer and Redfield propagation journal January 2019
Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling journal January 2020
Diabatic Hamiltonian construction in van der Waals heterostructure complexes journal January 2019
Explicit construction of diabatic state and its application to the direct evaluation of electronic coupling journal July 2018
Biological Relevance of Charge Transfer Branching Pathways in Photolyases journal March 2019
Diabatic Hamiltonian Construction in van der Waals heterostructure complexes preprint January 2019
Biological relevance of charge transfer branching pathways in photolyases text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
charge transfer integrals
density functional theory
electron transfer