Deuteration as a Means to Tune Crystallinity of Conducting Polymers

Jakowski, Jacek; Huang, Jingsong; Garashchuk, Sophya; Luo, Yingdong; Hong, Kunlun; Keum, Jong; Sumpter, Bobby G.

doi:10.1021/acs.jpclett.7b01803

Title: Deuteration as a Means to Tune Crystallinity of Conducting Polymers

Journal Article · Fri Aug 25 00:00:00 EDT 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b01803· OSTI ID:1394393

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^[1]; Garashchuk, Sophya ^[2]; Luo, Yingdong ^[1];

^[1]; Keum, Jong ^[1];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of South Carolina, Columbia, SC (United States)

The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied in this paper experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of the dipole fluctuations. The quantum molecular dynamics simulations confirm the interchain correlation of the proton–proton and deuteron–deuteron motions but not of the proton–deuteron motion. Thus and finally, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); ORNL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; CHE-1565985; CHE-1048629

OSTI ID:: 1394393

Journal Information:: Journal of Physical Chemistry Letters, Vol. 8, Issue 18; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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References (23)

Deuterium Labeling for Neutron Structure-Function-Dynamics Analysis Meilleur, Flora; Weiss, Kevin L.; Myles, Dean A. A. Micro and Nano Technologies in Bioanalysis https://doi.org/10.1007/978-1-59745-483-4_18	book	January 2009
Effect of Deuterium Substitution on the Physical Properties of Polymer Melts and Blends White, Ronald P.; Lipson, Jane E. G.; Higgins, Julia S. Macromolecules, Vol. 43, Issue 9 https://doi.org/10.1021/ma902707u	journal	May 2010
The isotopic effects of deuteration on optoelectronic properties of conducting polymers Shao, Ming; Keum, Jong; Chen, Jihua Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4180	journal	January 2014
Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya Journal of Chemical Theory and Computation, Vol. 12, Issue 9 https://doi.org/10.1021/acs.jctc.6b00126	journal	August 2016
Polymer semiconductor crystals Lim, Jung Ah; Liu, Feng; Ferdous, Sunzida Materials Today, Vol. 13, Issue 5 https://doi.org/10.1016/S1369-7021(10)70080-8	journal	May 2010
High Crystallinity and Nature of Crystal−Crystal Phase Transformations in Regioregular Poly(3-hexylthiophene) Pascui, Ovidiu F.; Lohwasser, Ruth; Sommer, Michael Macromolecules, Vol. 43, Issue 22 https://doi.org/10.1021/ma102205t	journal	November 2010
Controlling Poly(3-hexylthiophene) Crystal Dimension: Nanowhiskers and Nanoribbons Liu, Jianhua; Arif, Mohammad; Zou, Jianhua Macromolecules, Vol. 42, Issue 24 https://doi.org/10.1021/ma901955c	journal	December 2009
C–H Functionalization Polycondensation of Chlorothiophenes in the Presence of Nickel Catalyst with Stoichiometric or Catalytically Generated Magnesium Amide Tamba, Shunsuke; Shono, Keisuke; Sugie, Atsushi Journal of the American Chemical Society, Vol. 133, Issue 25 https://doi.org/10.1021/ja2033525	journal	June 2011
Dipole−Dipole Interactions in Nanoparticle Superlattices Talapin, Dmitri V.; Shevchenko, Elena V.; Murray, Christopher B. Nano Letters, Vol. 7, Issue 5, p. 1213-1219 https://doi.org/10.1021/nl070058c	journal	May 2007
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
A Strategy for Revealing the Packing in Semicrystalline π-Conjugated Polymers: Crystal Structure of Bulk Poly-3-hexyl-thiophene (P3HT) Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie Angewandte Chemie International Edition, Vol. 51, Issue 44 https://doi.org/10.1002/anie.201205075	journal	October 2012
Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties Elstner, M.; Porezag, D.; Jungnickel, G. Physical Review B, Vol. 58, Issue 11, p. 7260-7268 https://doi.org/10.1103/PhysRevB.58.7260	journal	September 1998
Implementation and benchmark tests of the DFTB method and its application in the ONIOM method Zheng, Guishan; Lundberg, Marcus; Jakowski, Jacek International Journal of Quantum Chemistry, Vol. 109, Issue 9 https://doi.org/10.1002/qua.22002	journal	January 2009
The vibrational spectrum of the hydrated proton: Comparison of experiment, simulation, and normal mode analysis Kim, Jeongho; Schmitt, Udo W.; Gruetzmacher, Julie A. The Journal of Chemical Physics, Vol. 116, Issue 2 https://doi.org/10.1063/1.1423327	journal	January 2002
Systematic study of vibrational frequencies calculated with the self-consistent charge density functional tight-binding method Witek, Henryk A.; Morokuma, Keiji Journal of Computational Chemistry, Vol. 25, Issue 15 https://doi.org/10.1002/jcc.20112	journal	November 2004
Relative Stability of Hydrogen and Deuterium Bonds Scheiner, Steve; Čuma, Martin Journal of the American Chemical Society, Vol. 118, Issue 6 https://doi.org/10.1021/ja9530376	journal	January 1996
A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states Rohrdanz, Mary A.; Martins, Katie M.; Herbert, John M. The Journal of Chemical Physics, Vol. 130, Issue 5 https://doi.org/10.1063/1.3073302	journal	February 2009
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method Colbert, Daniel T.; Miller, William H. The Journal of Chemical Physics, Vol. 96, Issue 3 https://doi.org/10.1063/1.462100	journal	February 1992
Comments on H/D Isotope Effects on Polarizabilities of Small Molecules. Correlation with Virial Coefficient, Molar Volume, and Electronic Second Moment Isotope Effects Van Hook, W. Alexander; Wolfsberg, Max Zeitschrift für Naturforschung A, Vol. 49, Issue 4-5 https://doi.org/10.1515/zna-1994-4-508	journal	May 1994
Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes Jeziorski, Bogumil; Moszynski, Robert; Szalewicz, Krzysztof Chemical Reviews, Vol. 94, Issue 7 https://doi.org/10.1021/cr00031a008	journal	November 1994
State of the Art and Challenges of the ab Initio Theory of Intermolecular Interactions Chałasiński, Grzegorz; Szczȩśniak, Małgorzata M. Chemical Reviews, Vol. 100, Issue 11 https://doi.org/10.1021/cr990048z	journal	November 2000

Cited By (3)

A fast scheme to calculate electronic couplings between P3HT polymer units using diabatic orbitals for charge transfer dynamics simulations Yu, Tao; Fabunmi, Florence; Huang, Jingsong Journal of Computational Chemistry, Vol. 40, Issue 2 https://doi.org/10.1002/jcc.25749	journal	December 2018
Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics Jakowski, Jacek; Huang, Jingsong; Sumpter, Bobby G. International Journal of Quantum Chemistry, Vol. 118, Issue 20 https://doi.org/10.1002/qua.25712	journal	September 2018
Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε‐Caprolactone) Li, Lengwan; Chang, Dongsook; Arras, Matthias M. L. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 12 https://doi.org/10.1002/polb.24831	journal	April 2019

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