Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems

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In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to pi-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole-and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase pi stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2018-04
Language
English
Article Type
Article
Keywords

MULLIKEN POPULATION ANALYSIS; TRANSITION CURRENT-DENSITY; ATOMIC BASIS-SETS; ORGANIC SEMICONDUCTORS; TRANSPORT; DIFFERENCE; PROTEINS; ENERGY; FORMULATION; PARAMETERS

Citation

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.20, no.14, pp.9146 - 9156

ISSN
1463-9076
DOI
10.1039/c8cp00266e
URI
http://hdl.handle.net/10203/241515
Appears in Collection
CH-Journal Papers(저널논문)
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