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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of South Carolina, Columbia, SC (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); ORNL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
OSTI Identifier:
1394393
Grant/Contract Number:  
AC05-00OR22725; CHE-1565985; CHE-1048629
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 18; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jakowski, Jacek, Huang, Jingsong, Garashchuk, Sophya, Luo, Yingdong, Hong, Kunlun, Keum, Jong, and Sumpter, Bobby G. Deuteration as a Means to Tune Crystallinity of Conducting Polymers. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpclett.7b01803.
Jakowski, Jacek, Huang, Jingsong, Garashchuk, Sophya, Luo, Yingdong, Hong, Kunlun, Keum, Jong, & Sumpter, Bobby G. Deuteration as a Means to Tune Crystallinity of Conducting Polymers. United States. https://doi.org/10.1021/acs.jpclett.7b01803
Jakowski, Jacek, Huang, Jingsong, Garashchuk, Sophya, Luo, Yingdong, Hong, Kunlun, Keum, Jong, and Sumpter, Bobby G. Fri . "Deuteration as a Means to Tune Crystallinity of Conducting Polymers". United States. https://doi.org/10.1021/acs.jpclett.7b01803. https://www.osti.gov/servlets/purl/1394393.
@article{osti_1394393,
title = {Deuteration as a Means to Tune Crystallinity of Conducting Polymers},
author = {Jakowski, Jacek and Huang, Jingsong and Garashchuk, Sophya and Luo, Yingdong and Hong, Kunlun and Keum, Jong and Sumpter, Bobby G.},
abstractNote = {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.},
doi = {10.1021/acs.jpclett.7b01803},
journal = {Journal of Physical Chemistry Letters},
number = 18,
volume = 8,
place = {United States},
year = {2017},
month = {8}
}

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    Works referencing / citing this record:

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