A cluster approach to the structure of imperfect materials and their relaxation spectroscopy

Abstract

A new theory is proposed for the explanation of observed relaxation phenomena, which differs significantly from theories suggested by the authors before. The theory is based on a model of structural organization of macroscopically sized samples of imperfectly structured materials, both solids and liquids, and is intermediate in character. In terms of the model, a microscopic structure is maintained over a cluster containing a number of microscopic units, with an array of clusters described by a steady-state distribution completing the macroscopic picture. The structural regularity of each level of morphological organization is precisely defined by a coarse-grained index, which is given a thermodynamic interpretation in terms of binding energies and configurational entropy. The limiting cases of an ideal liquid and a perfect crystal are recovered as asymptotic extremes in terms of this definition. The consequences of this model for the relaxation dynamics of the structure are examined and it is shown that prepared fluctuations decay in a time-power law manner as coupled zero-point motions evolve either within clusters or between clusters, with a power determined by the relevant regularity index. As a result, the origin of power law noise in materials is explained in terms of configurational entropy, and its relation with gaussian and white noise, which appear as asymptotic limits, outlined. The shape of the steady-state distribution of the array of clusters is also determined without any a priori assumptions, and it is shown to range from an unbounded form to a δ function as the regularity of the array superstructure increases. Experimental examples of dielectric relaxation spectroscopy have been used to illustrate these structural concepts and outline the way in which this technique can be used to deduce the structural organization of the sample. Finally, a short description is given of some commonly observed forms of response and their structural interpretation.