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

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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. 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. 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.

Original languageEnglish
Article numbere25712
JournalInternational Journal of Quantum Chemistry
Volume118
Issue number20
DOIs
StatePublished - Oct 15 2018

Funding

Part of this work was conducted at the Center for Nanophase Materials Sciences, a US Department of Energy Office of Science User Facility. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562 (allocation TG-DMR110037), and the HPC cluster, funded by the National Science Foundation under Grant No. CHE-1048629. This material is based upon work supported by the National Science Foundation under Grant Nos. CHE-1056188, CHE-1565985, and OIA-1655740, and by a GEAR grant from SC EPSCoR. National Science Foundation; US Department of Energy Office of Science information National Science Foundation; US Department of Energy Office of SciencePart of this work was conducted at the Center for Nanophase Materials Sciences, a US Department of Energy Office of Science User Facility. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant No. ACI-1548562 (allocation TG-DMR110037), and the HPC cluster, funded by the National Science Foundation under Grant No. CHE-1048629. This material is based upon work supported by the National Science Foundation under Grant Nos. CHE-1056188, CHE-1565985, and OIA-1655740, and by a GEAR grant from SC EPSCoR.

Keywords

  • dipole interactions
  • isotope effect on crystallinity
  • nuclear quantum effects
  • perturbation theory
  • quantum dynamics

Fingerprint

Dive into the research topics of 'Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics'. Together they form a unique fingerprint.

Cite this