Molecular dynamics in conducting polyaniline protonated by camphor sulfonic acid as seen by quasielastic neutron scattering

D. Djurado, J. Combet, M. Bée, P. Rannou, B. Dufour, A. Pron, and J. P. Travers
Phys. Rev. B 65, 184202 – Published 9 April 2002
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Abstract

Using incoherent quasielastic neutron scattering techniques, the molecular motions were investigated in fully hydrogenated and partially deuterated polyaniline protonated by camphor sulfonic acid (CSA) conducting samples. The obtained results show that on the 1091012s time scale the polymer chains do not exhibit any diffusive motions: the whole observed quasielastic scattering has accordingly to be attributed to motions of CSA ions. From our measurements two molecular movements could be differentiated. A rapid one has been attributed to the three-site rotation of methyl groups present on camphor moieties of CSA and a slower one that has been modeled as a rigid body motion of the whole CSA molecule. Due to the disordered character of the system, the methyl rotors appeared to be dynamically nonequivalent. Their dynamics was then described in terms of a log gaussian distribution of correlation times. This description allowed a good fitting of experimental data and gave an activation energy of 12.5 kJ mol1. However, two different regimes in temperature could be distinguished. At high temperatures (T>280K) the width of the distribution is nearly zero and thus, the methyl rotors are dynamically equivalent while it turned larger and larger when temperature is decreased below 250 K revealing that the rotors are more and more sensitive to their local environment. In the conducting samples the slowest motion clearly exists in the 280–330 K temperature range and is blocked at temperatures inferior to 250 K. This transition occurs in the temperature range in which the metal-insulator transition also happens.

  • Received 18 June 2001

DOI:https://doi.org/10.1103/PhysRevB.65.184202

©2002 American Physical Society

Authors & Affiliations

D. Djurado1,*, J. Combet2,†, M. Bée1,2, P. Rannou3, B. Dufour3, A. Pron3, and J. P. Travers3

  • 1Université J. Fourier, Grenoble I, Laboratoire de Spectrométrie Physique (UMR 5588-UJF-CNRS), Boîte Postale 87, 38402 St. Martin d’Hères-Cedex, France
  • 2Institut Laue Langevin, 6 rue Jules Horowitz, Boîte Postale 156, 38042 Grenoble-Cedex, France
  • 3Laboratoire de Physique des Métaux Synthétiques, UMR 5819 (CEA-UJF-CNRS), DRFMC, CEA, Grenoble 38054, Grenoble-Cedex 9, France

  • *Corresponding author. FAX: (33)4-76-635-495. Email address: David.Djurado@ujf.grenoble.fr
  • Permanent address: Institut Charles Sadron, 6, rue Boussingault, 67083 Strasbourg-Cedex, France.

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Vol. 65, Iss. 18 — 1 May 2002

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