Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

Larsen, Ross E.

doi:10.1021/acs.jpcc.6b02138

Title: Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

Journal Article · Tue Apr 12 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b02138· OSTI ID:1253911

Larsen, Ross E. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)

In this study, we introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parameterized from electronic structure calculations on monomers, dimers and, optionally, tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1253911

Report Number(s):: NREL/JA-2C00-65033

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 18; Related Information: Journal of Physical Chemistry C; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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Title: Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

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