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Title: Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics

Abstract

As seen in experiments with poly(3-hexylthiophene), substitution of hydrogen with deuterium on the main chain alone decreases crystallinity. To understand this effect, a general formalism for analysis of the dipole moments and polarizabilities incorporating quantum nuclei, is developed in this paper. The formalism, based on quantum dynamics of the proton/deuteron and on the perturbative analysis of the dipole interaction energy, accounts for the anharmonicity of a potential energy surface and for the anisotropy of molecular dipole moments. The formalism is implemented within the Discrete Variable Representation and the Density Functional Theory describing, respectively, the quantum proton/deuteron on the thiophene ring and the electronic structure of the 27-atom model polymer chain, embedded into a larger crystalline environment. Finally, the isotope effect is mainly attributed to the differences in the zero-point energy of the CH/CD bonds and to the isotope-dependence of the dipole-dipole inter-chain interactions.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering Division
  2. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1474697
Alternate Identifier(s):
OSTI ID: 1472182
Grant/Contract Number:  
AC05-00OR22725; ACI-1548562; CHE-1048629; CHE-1056188; CHE-1565985; OIA-1655740
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Quantum Chemistry
Additional Journal Information:
Journal Volume: 118; Journal Issue: 20; Journal ID: ISSN 0020-7608
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dipole interactions; isotope effect on crystallinity; nuclear quantum effects; perturbation theory; quantum dynamics

Citation Formats

Jakowski, Jacek, Huang, Jingsong, Sumpter, Bobby G., and Garashchuk, Sophya. Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics. United States: N. p., 2018. Web. doi:10.1002/qua.25712.
Jakowski, Jacek, Huang, Jingsong, Sumpter, Bobby G., & Garashchuk, Sophya. Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics. United States. doi:10.1002/qua.25712.
Jakowski, Jacek, Huang, Jingsong, Sumpter, Bobby G., and Garashchuk, Sophya. Sat . "Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics". United States. doi:10.1002/qua.25712. https://www.osti.gov/servlets/purl/1474697.
@article{osti_1474697,
title = {Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics},
author = {Jakowski, Jacek and Huang, Jingsong and Sumpter, Bobby G. and Garashchuk, Sophya},
abstractNote = {As seen in experiments with poly(3-hexylthiophene), substitution of hydrogen with deuterium on the main chain alone decreases crystallinity. To understand this effect, a general formalism for analysis of the dipole moments and polarizabilities incorporating quantum nuclei, is developed in this paper. The formalism, based on quantum dynamics of the proton/deuteron and on the perturbative analysis of the dipole interaction energy, accounts for the anharmonicity of a potential energy surface and for the anisotropy of molecular dipole moments. The formalism is implemented within the Discrete Variable Representation and the Density Functional Theory describing, respectively, the quantum proton/deuteron on the thiophene ring and the electronic structure of the 27-atom model polymer chain, embedded into a larger crystalline environment. Finally, the isotope effect is mainly attributed to the differences in the zero-point energy of the CH/CD bonds and to the isotope-dependence of the dipole-dipole inter-chain interactions.},
doi = {10.1002/qua.25712},
journal = {International Journal of Quantum Chemistry},
number = 20,
volume = 118,
place = {United States},
year = {2018},
month = {9}
}

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Figures / Tables:

Figure 1 Figure 1: A molecule with a single quantum nucleus, that is, the P3HT monomer with the thiophene bound proton (red) treated as the QM particle. Contours of the potential energy surface (PES), computed with DFT, are superimposed on the grid of the proton Cartesian coordinates. The arrow indicates the dipolemore » moment localized on the thiophene ring. The side chain exhibits negligible dipole moment. (B) A schematic representation of the interacting dipoles $D$$A$ and $D$$B$, separated by the distance $\mathcal{R}$ of the adjacent chains forming the P3HT crystal« less

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