Abstract
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. 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.
| Original language | English |
|---|---|
| Pages (from-to) | 532-542 |
| Number of pages | 11 |
| Journal | Journal of Computational Chemistry |
| Volume | 40 |
| Issue number | 2 |
| DOIs | |
| State | Published - Jan 15 2019 |
Funding
[a] T. Yu, F. Fabunmi Department of Chemistry, Tennessee Technological University, Cookeville, Tennessee, 38501 E-mail: [email protected] [b] J. Huang, B. G. Sumpter, J. Jakowski Center of Nanophase Materials Sciences & Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 37831 E-mail: [email protected] This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Contract Grant sponsor: Oak Ridge National Laboratory; Contract Grant number: ERKCZ01 This work was conducted at the Center for Nanophase Materials Sciences, a US Department of Energy Office of Science User Facility and was sponsored by the Laboratory Directed Research and Development (LDRD) Program of Oak Ridge National Laboratory. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562 (allocation TG-DMR110037). Tao Yu acknowledges the Department of Energy Visiting Faculty Program (VFP) at ORNL. Jacek Jakowski is grateful for the time spent at Emory University from 2007 to 2010 during which he collaborated with Prof. Keiji Morokuma on development of real-time Liouville-von Neumann electron dynamics and density functional tight binding approaches.
| Funders | Funder number |
|---|---|
| US Department of Energy Office of Science | |
| National Science Foundation | |
| U.S. Department of Energy | |
| Oak Ridge National Laboratory | ERKCZ01 |
| Laboratory Directed Research and Development |
Keywords
- DFT
- band structure
- conducting polymers
- electronic structure
- quantum dynamics
