Electronic Coupling Calculations for BridgeMediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and FragmentOrbital Density Functional Tight Binding (FODFTB) Level
In this paper, four methods to calculate charge transfer integrals in the context of bridgemediated 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 tightbinding DFT approach, using fragment orbitals) and two constrained DFT implementations with either planewave or local basis sets. To assess the performance of the methods for throughbond (TB)dominated or throughspace (TS)dominated transfer, different sets of molecules are considered. For throughbond electron transfer (ET), several molecules that were originally synthesized by PaddonRow and coworkers 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 throughspace ET, dedicated pstacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donoracceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragmentorbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponentialmore »
 Authors:

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 Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Physical Chemistry
 National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
 Univ. ParisSud, Orsay (France). Laboratoire de ChimiePhysique; Univ. ParisSaclay, Orsay (France); Centre National de la Recherche Scientifique (CNRS), Orsay (France)
 Univ. College London (United Kingdom). Dept. of Physics and Astronomy
 Publication Date:
 Report Number(s):
 NREL/JA270067308
Journal ID: ISSN 15499618
 Grant/Contract Number:
 AC3608GO28308; EP/L000202
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 15499618
 Publisher:
 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
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transfer integrals; electron transfer; density functional theory
 OSTI Identifier:
 1329526
Gillet, Natacha, Berstis, Laura, Wu, Xiaojing, Gajdos, Fruzsina, Heck, Alexander, de la Lande, Aurélien, Blumberger, Jochen, and Elstner, Marcus. Electronic Coupling Calculations for BridgeMediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and FragmentOrbital Density Functional Tight Binding (FODFTB) Level. United States: N. p.,
Web. doi:10.1021/acs.jctc.6b00564.
Gillet, Natacha, Berstis, Laura, Wu, Xiaojing, Gajdos, Fruzsina, Heck, Alexander, de la Lande, Aurélien, Blumberger, Jochen, & Elstner, Marcus. Electronic Coupling Calculations for BridgeMediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and FragmentOrbital Density Functional Tight Binding (FODFTB) Level. United States. doi:10.1021/acs.jctc.6b00564.
Gillet, Natacha, Berstis, Laura, Wu, Xiaojing, Gajdos, Fruzsina, Heck, Alexander, de la Lande, Aurélien, Blumberger, Jochen, and Elstner, Marcus. 2016.
"Electronic Coupling Calculations for BridgeMediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and FragmentOrbital Density Functional Tight Binding (FODFTB) Level". United States.
doi:10.1021/acs.jctc.6b00564. https://www.osti.gov/servlets/purl/1329526.
@article{osti_1329526,
title = {Electronic Coupling Calculations for BridgeMediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and FragmentOrbital Density Functional Tight Binding (FODFTB) Level},
author = {Gillet, Natacha and Berstis, Laura and Wu, Xiaojing and Gajdos, Fruzsina and Heck, Alexander and de la Lande, Aurélien and Blumberger, Jochen and Elstner, Marcus},
abstractNote = {In this paper, four methods to calculate charge transfer integrals in the context of bridgemediated 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 tightbinding DFT approach, using fragment orbitals) and two constrained DFT implementations with either planewave or local basis sets. To assess the performance of the methods for throughbond (TB)dominated or throughspace (TS)dominated transfer, different sets of molecules are considered. For throughbond electron transfer (ET), several molecules that were originally synthesized by PaddonRow and coworkers 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 throughspace ET, dedicated pstacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donoracceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragmentorbital 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 donoracceptor 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 longrange charge transfers.},
doi = {10.1021/acs.jctc.6b00564},
journal = {Journal of Chemical Theory and Computation},
number = 10,
volume = 12,
place = {United States},
year = {2016},
month = {9}
}