The dielectric response of simple organic glass formers

• Published in: Journal of molecular structure Vol. 479; no. 2; pp. 201 - 218
• Main Authors: Kudlik, A., Benkhof, S., Blochowicz, T., Tschirwitz, C., Rössler, E.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 27-04-1999
• Subjects: Dielectric spectroscopy; Glass transition; Organic liquids; Glass transition; Organic liquids; Dielectric spectroscopy
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/S0022-2860(98)00871-0

After a short historical review concerning measurements of the dielectric response of simple glass formers, we discuss the complex dielectric permittivity
ε
̂
ν
above and below the glass transition temperature,
T
g, which we investigated in the frequency range 10
−3
Hz<ν<10
9
Hz. (i) As a first group of glass formers (type A systems) glycerol and propylene carbonate, which do not show a β-process, were studied, and a complete line-shape analysis of
ε
̂
ν
is presented. The evolution of the high-frequency wing of the main relaxation (
α-process) is the most prominent spectral change while cooling and leads to an essentially constant loss at
T<
T
g. This yields approximately a “1/
f noise” in the spectral density, which extends at least over 7
decades in frequency (10
−2 Hz<ν<10
5 Hz). (ii) Several glass formers exhibit a pronounced β-relaxation in addition to the α-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 line-shape analysis is carried out including both processes by applying the Williams–Watts (WW) approach. Compiling several properties of the β-relaxation, that are generally observed, we give new arguments supporting Johari’s idea, that the β-process is an intrinsic property of supercooled liquids, although its relaxation strength may vary significantly among different glass formers. In some cases even no discernible β-process is observed (type A systems). Within the WW approach, we interpret the β-process as a local, spatially restricted reorientational process which precedes the α-relaxation. Above
T
g, its relaxation strength strongly increases with temperature indicating that the spatial restriction imposed on the β-process reorientation is released upon emergence of the α-process.