Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene

Sudipta Gupta; Sourav Chatterjee; Piotr Zolnierczuk; Evgueni E. Nesterov; Gerald J. Schneider

doi:10.1038/s41598-020-66354-6

Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene

Sudipta Gupta, Sourav Chatterjee, Piotr Zolnierczuk, Evgueni E. Nesterov, Gerald J. Schneider

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

We exploited the high temporal and spatial resolution of neutron spin echo spectroscopy to investigate the large-scale dynamics of semiflexible conjugated polymer chains in solutions. We used a generalized approach of the well-established Zimm model of flexible polymers to describe the relaxation mode spectra of locally stiff polythiophene chains. The Zimm mode analysis confirms the existence of beads with a finite length that corresponds to a reduced number of segmental modes in semiflexible chains. Irrespective of the temperature and the molecular weight of the conjugated polymer, we witness a universal behavior of the local chain stiffness and invariability of the bead length. Our experimental findings indicate possibly minor role of the change in π-electron conjugation length (and therefore conjugated backbone planar to non-planar conformational transition) in the observed thermochromic behavior of polythiophene but instead point on the major role of chain dynamics in this phenomenon. We also obtained the first experimental evidence of an existence of a single-chain glass state in conjugated polymers.

Original language	English
Article number	9966
Journal	Scientific Reports
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41598-020-66354-6
State	Published - Dec 1 2020
Externally published	Yes

Funding

The neutron scattering work was supported by the U.S. Department of Energy (DOE) under EPSCoR Grant No. DE-SC0012432 with additional support from the Louisiana Board of Regents. Research conducted at ORNL’s High Flux Isotope Reactor (HFIR) and at Spallation Neutron Source (SNS) was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy (DoE). We thank Lilin He (HFIR), Marius Hofmann (LSU), Stefan Otto Huber (LSU) and Christopher Van Leeuwen (LSU) for helping with the scattering experiments.

Funders	Funder number
Office of Basic Energy Sciences
Scientific User Facilities Division
U.S. Department of Energy
Office of Experimental Program to Stimulate Competitive Research
Basic Energy Sciences	DE-SC0012432

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title = "Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene",

abstract = "We exploited the high temporal and spatial resolution of neutron spin echo spectroscopy to investigate the large-scale dynamics of semiflexible conjugated polymer chains in solutions. We used a generalized approach of the well-established Zimm model of flexible polymers to describe the relaxation mode spectra of locally stiff polythiophene chains. The Zimm mode analysis confirms the existence of beads with a finite length that corresponds to a reduced number of segmental modes in semiflexible chains. Irrespective of the temperature and the molecular weight of the conjugated polymer, we witness a universal behavior of the local chain stiffness and invariability of the bead length. Our experimental findings indicate possibly minor role of the change in π-electron conjugation length (and therefore conjugated backbone planar to non-planar conformational transition) in the observed thermochromic behavior of polythiophene but instead point on the major role of chain dynamics in this phenomenon. We also obtained the first experimental evidence of an existence of a single-chain glass state in conjugated polymers.",

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AU - Zolnierczuk, Piotr

AU - Nesterov, Evgueni E.

AU - Schneider, Gerald J.

PY - 2020/12/1

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N2 - We exploited the high temporal and spatial resolution of neutron spin echo spectroscopy to investigate the large-scale dynamics of semiflexible conjugated polymer chains in solutions. We used a generalized approach of the well-established Zimm model of flexible polymers to describe the relaxation mode spectra of locally stiff polythiophene chains. The Zimm mode analysis confirms the existence of beads with a finite length that corresponds to a reduced number of segmental modes in semiflexible chains. Irrespective of the temperature and the molecular weight of the conjugated polymer, we witness a universal behavior of the local chain stiffness and invariability of the bead length. Our experimental findings indicate possibly minor role of the change in π-electron conjugation length (and therefore conjugated backbone planar to non-planar conformational transition) in the observed thermochromic behavior of polythiophene but instead point on the major role of chain dynamics in this phenomenon. We also obtained the first experimental evidence of an existence of a single-chain glass state in conjugated polymers.

AB - We exploited the high temporal and spatial resolution of neutron spin echo spectroscopy to investigate the large-scale dynamics of semiflexible conjugated polymer chains in solutions. We used a generalized approach of the well-established Zimm model of flexible polymers to describe the relaxation mode spectra of locally stiff polythiophene chains. The Zimm mode analysis confirms the existence of beads with a finite length that corresponds to a reduced number of segmental modes in semiflexible chains. Irrespective of the temperature and the molecular weight of the conjugated polymer, we witness a universal behavior of the local chain stiffness and invariability of the bead length. Our experimental findings indicate possibly minor role of the change in π-electron conjugation length (and therefore conjugated backbone planar to non-planar conformational transition) in the observed thermochromic behavior of polythiophene but instead point on the major role of chain dynamics in this phenomenon. We also obtained the first experimental evidence of an existence of a single-chain glass state in conjugated polymers.

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Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene

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