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Chain and local dynamics of polyisoprene as probed by experiments and computer simulations

J. Chem. Phys. 119, 6883 (2003); doi:10.1063/1.1603720

Issue Date: 1 October 2003

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M. Doxastakis
F.O.R.T.H.-Institute of Chemical Engineering and High-Temperature Chemical Processes, P.O. Box 1414, 26504 Patras, Greece
F.O.R.T.H.-Institute of Electronic Structure and Laser, P.O. Box 1527, Heraklion, Crete, Greece

D. N. Theodorou
F.O.R.T.H.-Institute of Chemical Engineering and High-Temperature Chemical Processes, P.O. Box 1414, 26504 Patras, Greece

G. Fytas
F.O.R.T.H.-Institute of Electronic Structure and Laser, P.O. Box 1527, Heraklion, Crete, Greece
Max-Planck Institut für Polymerforschung, P.O. Box 3148, D-55021 Mainz, Germany

F. Kremer
Department of Physics, University of Leipzig, D-04103, Leipzig, Germany

R. Faller and F. Müller-Plathe
Max-Planck Institut für Polymerforschung, P.O. Box 3148, D-55021 Mainz, Germany

N. Hadjichristidis
Department of Chemistry, University of Athens, 15701 Zografou, Athens, Greece
F.O.R.T.H.-Institute of Electronic Structure and Laser, P.O. Box 1527, Heraklion, Crete, Greece
The dynamics of designed short polyisoprene (PI) chains in the melt is investigated on a wide temperature window using dielectric relaxation spectroscopy and pulsed field gradient nuclear magnetic resonance (NMR). At high temperatures, molecular dynamics (MD) simulations performed using two different models (an explicit atom model and a united atom one) capture very well the dynamic properties documented experimentally. Structures pre-equilibrated with end-bridging Monte Carlo are used as initial configurations for MD runs at different temperatures, providing predictions for the temperature dependence of the dynamics of this bulk PI. Local dynamics is unique, independently of the probe (dielectric relaxation, dynamic light scattering, nuclear magnetic resonance, neutron scattering), although mean correlation times are significantly affected, to different extents, by librations. Chain dynamics over the molecular weight and temperature range studied can be described well by the Rouse model, as shown by both experimental data and a normal mode analysis on simulation trajectories. Deviations from the Rouse model emerge for the high modes at short times; still, this model offers a rather accurate picture. ©2003 American Institute of Physics.
History: Received 21 May 2003; accepted 1 July 2003
Permalink: http://link.aip.org/link/?JCPSA6/119/6883/1
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KEYWORDS and PACS

Keywords
PACS
  • 61.25.Hq
    Structure of macromolecular and polymer solutions, and polymer melts; swelling
  • 76.60.-k
    Nuclear magnetic resonance and relaxation (condensed matter)
  • 61.20.Ja
    Computer simulation of liquid structure
  • 77.22.Gm
    Dielectric loss and relaxation
  • 61.12.Ex
    Neutron scattering (including small-angle scattering)
  • YEAR: 2003

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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