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

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. 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.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [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
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1488703
Alternate Identifier(s):
OSTI ID: 1485692
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Computational Chemistry
Additional Journal Information:
Journal Volume: 40; Journal Issue: 2; Journal ID: ISSN 0192-8651
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; band structure; electronic structure; quantum dynamics; DFT; conducting polymers

Citation Formats

Yu, Tao, Fabunmi, Florence, Huang, Jingsong, Sumpter, Bobby G., and Jakowski, Jacek. A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations. United States: N. p., 2018. Web. doi:10.1002/jcc.25749.
Yu, Tao, Fabunmi, Florence, Huang, Jingsong, Sumpter, Bobby G., & Jakowski, Jacek. A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations. United States. doi:10.1002/jcc.25749.
Yu, Tao, Fabunmi, Florence, Huang, Jingsong, Sumpter, Bobby G., and Jakowski, Jacek. Wed . "A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations". United States. doi:10.1002/jcc.25749. https://www.osti.gov/servlets/purl/1488703.
@article{osti_1488703,
title = {A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations},
author = {Yu, Tao and Fabunmi, Florence and Huang, Jingsong and Sumpter, Bobby G. and Jakowski, Jacek},
abstractNote = {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.},
doi = {10.1002/jcc.25749},
journal = {Journal of Computational Chemistry},
number = 2,
volume = 40,
place = {United States},
year = {2018},
month = {12}
}

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Works referenced in this record:

Implementation and benchmark tests of the DFTB method and its application in the ONIOM method
journal, January 2009

  • Zheng, Guishan; Lundberg, Marcus; Jakowski, Jacek
  • International Journal of Quantum Chemistry, Vol. 109, Issue 9
  • DOI: 10.1002/qua.22002

The Structure of Electronic Excitation Levels in Insulating Crystals
journal, August 1937


Preparation of thermostable and electric-conducting poly(2,5-thienylene)
journal, January 1980

  • Yamamoto, Takakazu; Sanechika, Kenichi; Yamamoto, Akio
  • Journal of Polymer Science: Polymer Letters Edition, Vol. 18, Issue 1
  • DOI: 10.1002/pol.1980.130180103

Charge Trapping at the Step Edges of TiO 2 Anatase (101)
journal, March 2014

  • Setvin, Martin; Hao, Xianfeng; Daniel, Benjamin
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201309796

Electronic-Structure Theory of Organic Semiconductors: Charge-Transport Parameters and Metal/Organic Interfaces
journal, July 2013


Density functional tight binding: values of semi-empirical methods in an ab initio era
journal, January 2014

  • Cui, Qiang; Elstner, Marcus
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/C4CP00908H

Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals
journal, September 1969

  • Hehre, W. J.; Stewart, R. F.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 51, Issue 6
  • DOI: 10.1063/1.1672392

Charge Transport in Organic Semiconductors
journal, April 2007

  • Coropceanu, Veaceslav; Cornil, Jérôme; da Silva Filho, Demetrio A.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr050140x

Probing Charge Transport in π-Stacked Fluorene-Based Systems
journal, May 2006

  • Coropceanu, Veaceslav; Nakano, Tamaki; Gruhn, Nadine E.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 19
  • DOI: 10.1021/jp060855j

Time-dependent quantum dynamical simulations of C 2 condensation under extreme conditions
journal, January 2012

  • Jakowski, Jacek; Irle, Stephan; Morokuma, Keiji
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 18
  • DOI: 10.1039/C1CP22035G

A Strategy for Revealing the Packing in Semicrystalline π-Conjugated Polymers: Crystal Structure of Bulk Poly-3-hexyl-thiophene (P3HT)
journal, October 2012

  • Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie
  • Angewandte Chemie International Edition, Vol. 51, Issue 44
  • DOI: 10.1002/anie.201205075

Dynamical Simulation of Electron Transfer Processes in Alkanethiolate Self-Assembled Monolayers at the Au(111) Surface
journal, November 2013

  • Prucker, Veronika; Rubio-Pons, Oscar; Bockstedte, Michel
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp4091848

Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections
journal, August 2016

  • Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 9
  • DOI: 10.1021/acs.jctc.6b00126

Two‐layer organic photovoltaic cell
journal, January 1986

  • Tang, C. W.
  • Applied Physics Letters, Vol. 48, Issue 2
  • DOI: 10.1063/1.96937

Functionalized Acenes and Heteroacenes for Organic Electronics
journal, December 2006


Effect of Electronic Polarization on Charge-Transport Parameters in Molecular Organic Semiconductors
journal, August 2006

  • Valeev, Edward F.; Coropceanu, Veaceslav; da Silva Filho, Demetrio A.
  • Journal of the American Chemical Society, Vol. 128, Issue 30
  • DOI: 10.1021/ja061827h

Voltage Losses in Organic Solar Cells: Understanding the Contributions of Intramolecular Vibrations to Nonradiative Recombinations
journal, December 2017


Modeling Charge Transfer in Fullerene Collisions via Real-Time Electron Dynamics
journal, May 2012

  • Jakowski, Jacek; Irle, Stephan; Sumpter, Bobby G.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 11
  • DOI: 10.1021/jz3004377

Liouville–von Neumann molecular dynamics
journal, June 2009

  • Jakowski, Jacek; Morokuma, Keiji
  • The Journal of Chemical Physics, Vol. 130, Issue 22
  • DOI: 10.1063/1.3152120

Effect of annealing on the electronic structure of poly(3-hexylthiophene) thin film
journal, January 2010

  • Kanai, Kaname; Miyazaki, Takahiro; Suzuki, Hiroyuki
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 1
  • DOI: 10.1039/B914100F

Crystal step edges can trap electrons on the surfaces of n-type organic semiconductors
journal, May 2018


Polymer semiconductor crystals
journal, May 2010


Deuteration as a Means to Tune Crystallinity of Conducting Polymers
journal, August 2017

  • Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 18
  • DOI: 10.1021/acs.jpclett.7b01803

Density functional tight binding
journal, March 2014

  • Elstner, Marcus; Seifert, Gotthard
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011
  • DOI: 10.1098/rsta.2012.0483

Poly(3-hexylthiophene): synthetic methodologies and properties in bulk heterojunction solar cells
journal, January 2012

  • Marrocchi, Assunta; Lanari, Daniela; Facchetti, Antonio
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee22129b

Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets
journal, April 1984

  • Frisch, Michael J.; Pople, John A.; Binkley, J. Stephen
  • The Journal of Chemical Physics, Vol. 80, Issue 7
  • DOI: 10.1063/1.447079

Analytic Properties of Bloch Waves and Wannier Functions
journal, August 1959


Orthogonal Orbitals and Generalized Wannier Functions
journal, January 1963


π-Conjugated Polymers for Organic Electronics and Photovoltaic Cell Applications
journal, February 2011


Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups
journal, December 2012

  • Li, Jingrui; Wang, Haobin; Persson, Petter
  • The Journal of Chemical Physics, Vol. 137, Issue 22
  • DOI: 10.1063/1.4746768

Organic photovoltaics
journal, January 2009

  • Kippelen, Bernard; Brédas, Jean-Luc
  • Energy & Environmental Science, Vol. 2, Issue 3
  • DOI: 10.1039/b812502n

An experimental and computational study of donor-linker-acceptor block copolymers for organic photovoltaics
journal, August 2018

  • Hu, Zhiqi; Jakowski, Jacek; Zheng, Chenyu
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 16
  • DOI: 10.1002/polb.24633

Density functional tight binding: application to organic and biological molecules: Density functional tight binding
journal, June 2013

  • Gaus, Michael; Cui, Qiang; Elstner, Marcus
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1
  • DOI: 10.1002/wcms.1156

On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals
journal, March 1950

  • Löwdin, Per‐Olov
  • The Journal of Chemical Physics, Vol. 18, Issue 3
  • DOI: 10.1063/1.1747632

Self‐Consistent Molecular Orbital Methods. XIII. An Extended Gaussian‐Type Basis for Boron
journal, April 1972

  • Hehre, W. J.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 8
  • DOI: 10.1063/1.1677844

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527