Orientational relaxations in solid (1,1,2,2)tetrachloroethane
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We employ dielectricspectroscopy and molecular dynamic simulations to investigate the dipolar dynamics in the orientationally disordered solid phase of (1,1,2,2)tetrachloroethane. Three distinct orientational dynamics are observed as separate dielectric loss features, all characterized by a simply activated temperature dependence. The slower process, associated to a glassytransition at 156 ± 1 K, corresponds to a cooperative motion by which each molecule rotates by 180° around the molecular symmetry axis through an intermediate state in which the symmetry axis is oriented roughly orthogonally to the initial and final states. Of the other two dipolar relaxations, the intermediate one is the Johari-Goldstein precursor relaxation of the cooperative dynamics, while the fastest process corresponds to an orientational fluctuation of single molecules into a higher-energy orientation. The Kirkwood correlation factor of the cooperative relaxation is of the order of one tenth, indicating that the molecular dipoles maintain on average a strong antiparallel alignment during their collective motion. These findings show that the combination of dielectricspectroscopy and molecular simulations allows studying in great detail the orientational dynamics in molecular solids.
CitationTripathi, P., Mitsari, E., Romanini, M., Serra, P., Tamarit, J. Ll., Zuriaga, J., Macovez, R. Orientational relaxations in solid (1,1,2,2)tetrachloroethane. "Journal of chemical physics", 2016, vol. 144.