Orientation relaxation in glassy polymers. II. Dipole-size spectroscopy and short-time kinetics

Alexander Z. Patashinski, Mark A Ratner

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The orientational diffusion of a rodlike particle embedded in a glassy polymeric matrix is considered; the underlying kinetics is that of local rearrangements. A defining parameter of the theory is the length of the particle. The timing of steps of the random walk in orientation space is determined by rearrangements. We discuss the physical properties of the glass state in connection with the rearrangement kinetics. The orientational diffusion is influenced by the local disorder; this influence is different for dipoles of different length. For a short dipole, the resulting diffusion is of generalized Debye type. Nonexponential relaxation of physical quantities may then be caused by the distribution of rearrangement barriers. For longer dipoles and if the orientation is uniquely determined by the configuration of the embedding cluster, the motion is a random walk on a given random map on a sphere. An ensemble of random mappings is considered. For even longer dipoles, hierarchical (multiscale) relaxation is expected. We discuss the relation of the theory to the short time depoling kinetics in a system of dipoles having different length, such as are found in relaxation of electrically poled polymer materials.

Original languageEnglish
Pages (from-to)10779-10789
Number of pages11
JournalJournal of Chemical Physics
Volume103
Issue number24
Publication statusPublished - 1995

Fingerprint

Polymers
Spectroscopy
dipoles
Kinetics
kinetics
polymers
spectroscopy
random walk
space orientation
Physical properties
Glass
embedding
physical properties
time measurement
disorders
glass
matrices
configurations

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Orientation relaxation in glassy polymers. II. Dipole-size spectroscopy and short-time kinetics. / Patashinski, Alexander Z.; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 103, No. 24, 1995, p. 10779-10789.

Research output: Contribution to journalArticle

@article{b0903778f84c4cc399cd71fe6400efdc,
title = "Orientation relaxation in glassy polymers. II. Dipole-size spectroscopy and short-time kinetics",
abstract = "The orientational diffusion of a rodlike particle embedded in a glassy polymeric matrix is considered; the underlying kinetics is that of local rearrangements. A defining parameter of the theory is the length of the particle. The timing of steps of the random walk in orientation space is determined by rearrangements. We discuss the physical properties of the glass state in connection with the rearrangement kinetics. The orientational diffusion is influenced by the local disorder; this influence is different for dipoles of different length. For a short dipole, the resulting diffusion is of generalized Debye type. Nonexponential relaxation of physical quantities may then be caused by the distribution of rearrangement barriers. For longer dipoles and if the orientation is uniquely determined by the configuration of the embedding cluster, the motion is a random walk on a given random map on a sphere. An ensemble of random mappings is considered. For even longer dipoles, hierarchical (multiscale) relaxation is expected. We discuss the relation of the theory to the short time depoling kinetics in a system of dipoles having different length, such as are found in relaxation of electrically poled polymer materials.",
author = "Patashinski, {Alexander Z.} and Ratner, {Mark A}",
year = "1995",
language = "English",
volume = "103",
pages = "10779--10789",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "24",

}

TY - JOUR

T1 - Orientation relaxation in glassy polymers. II. Dipole-size spectroscopy and short-time kinetics

AU - Patashinski, Alexander Z.

AU - Ratner, Mark A

PY - 1995

Y1 - 1995

N2 - The orientational diffusion of a rodlike particle embedded in a glassy polymeric matrix is considered; the underlying kinetics is that of local rearrangements. A defining parameter of the theory is the length of the particle. The timing of steps of the random walk in orientation space is determined by rearrangements. We discuss the physical properties of the glass state in connection with the rearrangement kinetics. The orientational diffusion is influenced by the local disorder; this influence is different for dipoles of different length. For a short dipole, the resulting diffusion is of generalized Debye type. Nonexponential relaxation of physical quantities may then be caused by the distribution of rearrangement barriers. For longer dipoles and if the orientation is uniquely determined by the configuration of the embedding cluster, the motion is a random walk on a given random map on a sphere. An ensemble of random mappings is considered. For even longer dipoles, hierarchical (multiscale) relaxation is expected. We discuss the relation of the theory to the short time depoling kinetics in a system of dipoles having different length, such as are found in relaxation of electrically poled polymer materials.

AB - The orientational diffusion of a rodlike particle embedded in a glassy polymeric matrix is considered; the underlying kinetics is that of local rearrangements. A defining parameter of the theory is the length of the particle. The timing of steps of the random walk in orientation space is determined by rearrangements. We discuss the physical properties of the glass state in connection with the rearrangement kinetics. The orientational diffusion is influenced by the local disorder; this influence is different for dipoles of different length. For a short dipole, the resulting diffusion is of generalized Debye type. Nonexponential relaxation of physical quantities may then be caused by the distribution of rearrangement barriers. For longer dipoles and if the orientation is uniquely determined by the configuration of the embedding cluster, the motion is a random walk on a given random map on a sphere. An ensemble of random mappings is considered. For even longer dipoles, hierarchical (multiscale) relaxation is expected. We discuss the relation of the theory to the short time depoling kinetics in a system of dipoles having different length, such as are found in relaxation of electrically poled polymer materials.

UR - http://www.scopus.com/inward/record.url?scp=0000896047&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000896047&partnerID=8YFLogxK

M3 - Article

VL - 103

SP - 10779

EP - 10789

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 24

ER -