The dielectric response of simple organic glass formers

Citation
A. Kudlik et al., The dielectric response of simple organic glass formers, J MOL STRUC, 479(2-3), 1999, pp. 201-218
Citations number
93
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF MOLECULAR STRUCTURE
ISSN journal
00222860 → ACNP
Volume
479
Issue
2-3
Year of publication
1999
Pages
201 - 218
Database
ISI
SICI code
0022-2860(19990427)479:2-3<201:TDROSO>2.0.ZU;2-Q
Abstract
After a short historical review concerning measurements of the dielectric r esponse of simple glass formers, we discuss the complex dielectric permitti vity <(epsilon)over cap> (nu) above and below the glass transition temperat ure, T-g, which we investigated in the frequency range 10(-3) Hz < nu < 10( 9) Hz. (i) As a first group of glass formers (type A systems) glycerol and propylene carbonate, which do not show a beta-process, were studied, and a complete line-shape analysis of <(epsilon)over cap>(nu) is presented. The e volution of the high-frequency wing of the main relaxation (alpha-process) is the most prominent spectral change while cooling and leads to an essenti ally constant loss at T < T-g. This yields approximately a "1/f noise" in t he spectral density, which extends at least over 7 decades in frequency (10 (-2) Hz < nu < 10(5) Hz). (ii) Several glass formers exhibit a pronounced b eta-relaxation in addition to the alpha-process (type B systems). Of these we investigated the dielectrically rigid systems toluene and fluoroaniline, as well as propanol and polybutadiene. The high-frequency wing observed in type A systems seems to reoccur also in type B systems. A quantitative lin e-shape analysis is carried out including both processes by applying the Wi lliams-Watts (WW) approach. Compiling several properties of the beta-relaxa tion, that are generally observed, we give new arguments supporting Johari' s idea, that the beta-process is an intrinsic property of supercooled liqui ds, although its relaxation strength may vary significantly among different glass formers. In some cases even no discernible beta-process is observed (type A systems). Within the WW approach, we interpret the beta-process as a local, spatially restricted reorientational process which precedes the al pha-relaxation. Above T-g, its relaxation strength strongly increases with temperature indicating that the spatial restriction imposed on the beta-pro cess reorientation is released upon emergence of the alpha-process. (C) 199 9 Elsevier Science B.V. All rights reserved.