Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers
Abstract
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.
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
- OSTI Identifier:
- 1253911
- Report Number(s):
- NREL/JA-2C00-65033
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 18; Related Information: Journal of Physical Chemistry C; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; electronic structure; donor-acceptor copolymer; organic photovoltaics; polythiophene; Huckel theory; tight binding; effective Hamiltonian; frontier molecular orbitals
Citation Formats
Larsen, Ross E. Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b02138.
Larsen, Ross E. Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers. United States. https://doi.org/10.1021/acs.jpcc.6b02138
Larsen, Ross E. Tue .
"Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers". United States. https://doi.org/10.1021/acs.jpcc.6b02138. https://www.osti.gov/servlets/purl/1253911.
@article{osti_1253911,
title = {Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers},
author = {Larsen, Ross E.},
abstractNote = {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.},
doi = {10.1021/acs.jpcc.6b02138},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 120,
place = {United States},
year = {Tue Apr 12 00:00:00 EDT 2016},
month = {Tue Apr 12 00:00:00 EDT 2016}
}
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