Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics
As seen in experiments with poly(3hexylthiophene), 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 27atom model polymer chain, embedded into a larger crystalline environment. Finally, the isotope effect is mainly attributed to the differences in the zeropoint energy of the CH/CD bonds and to the isotopedependence of the dipoledipole interchain interactions.
 Authors:

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 Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering Division
 Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
 Publication Date:
 Grant/Contract Number:
 AC0500OR22725; ACI1548562; CHE1048629; CHE1056188; CHE1565985; OIA1655740
 Type:
 Accepted Manuscript
 Journal Name:
 International Journal of Quantum Chemistry
 Additional Journal Information:
 Journal Name: International Journal of Quantum Chemistry; Journal ID: ISSN 00207608
 Publisher:
 Wiley
 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)
 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
 OSTI Identifier:
 1474697
 Alternate Identifier(s):
 OSTI ID: 1472182
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.,
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. 2018.
"Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics". United States.
doi:10.1002/qua.25712.
@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(3hexylthiophene), 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 27atom model polymer chain, embedded into a larger crystalline environment. Finally, the isotope effect is mainly attributed to the differences in the zeropoint energy of the CH/CD bonds and to the isotopedependence of the dipoledipole interchain interactions.},
doi = {10.1002/qua.25712},
journal = {International Journal of Quantum Chemistry},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {9}
}
Works referenced in this record:
Semiempirical GGAtype density functional constructed with a longrange dispersion correction
journal, January 2006
journal, January 2006
 Grimme, Stefan
 Journal of Computational Chemistry, Vol. 27, Issue 15, p. 17871799