Disentangling the secondary relaxations in the orientationally disordered mixed crystals: cycloheptanol + cyclooctanol two-component system

Abstract

The dynamics of the pure compounds and mixed crystals formed between cycloheptanol (cC7-ol) and cyclooctanol (cC8-ol) has been studied by means of broadband dielectric spectroscopy at temperatures near and above the orientational glass transition temperature. Both compounds are known to display at least one orientationally disordered (OD) phase of simple cubic symmetry, and within this phase, a continuous formation of mixed crystals was demonstrated in the past (Rute, M. A. et al. J. Phys. Chem. B 2003, 107, 5914). The dielectric loss spectra of cC7-ol and cC8-ol show, in addition to the well-pronounced α-relaxation peaks with a continuous temperature shift (characteristic of the freezing of the molecular dynamics), secondary relaxations ( β and γ for cC8-ol and γ for cC7-ol) which are intramolecular in nature. The dynamics of several OD mixed crystals was recently studied (Singh, L. P.; Murthy, S. S. N. J. Phys. Chem. B 2008, 112, 2606), and surprisingly enough one of the secondary relaxations was not evidenced. We show here by means of a careful set of measurements for several mixed crystals and of a detailed analysis procedure the existence of the secondary relaxations for the mixed crystals. The results, moreover, doubtless reinforce the physical origin of each of the secondary relaxations.