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A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations

Journal Article · · Journal of Computational Chemistry
DOI:https://doi.org/10.1002/jcc.25749· OSTI ID:1488703
 [1];  [1];  [2];  [3];  [3]
  1. Tennessee Technological Univ., Cookeville, TN (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center of Nanophase Materials Sciences & Computational Sciences and Engineering Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center of Nanophase Materials Sciences & Computational Sciences and Engineering Division

We propose a fast and accurate calculation method to compute the electronic couplings between molecular units in a thiophene-ring-based polymer chain mimicking a real organic semiconducting polymer, poly(3-hexylthiophene). Through a unit block diabatization scheme, the method employed minimal number of diabatic orbitals to compute the site energies and electronic couplings, which were validated by comparing with benchmark density functional theory calculations. In addition, by using the obtained electronic couplings, a quantum dynamics simulation was carried out to propagate a hole initially localized in a thiophene-ring unit of the polymer chain. Here, this work establishes a simple, efficient, and robust means for the simulation of electron or hole transfer processes in organic semiconducting materials, an important capability for study and understanding of the class of organic optoelectronic and photovoltaic materials.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1488703
Alternate ID(s):
OSTI ID: 1485692
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Journal Issue: 2 Vol. 40; ISSN 0192-8651
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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