Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer

David O. López, Josep Salud, María Rosario de la Fuente, Nerea Sebastián, and Sergio Diez-Berart
Phys. Rev. E 97, 012704 – Published 17 January 2018

Abstract

In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (Tg) temperatures: The higher Tg is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (μ1L); the lower Tg is due to the motions responsible for the two relaxation modes with highest frequencies (μ1H and μ2), which converge just at their corresponding Tg. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (μ1L and μ1H) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (μ2) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (μ1H+μ2) presents a value of the steepness index and μ1L a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 34TNI.

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  • Received 28 July 2017

DOI:https://doi.org/10.1103/PhysRevE.97.012704

©2018 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied PhysicsGeneral PhysicsPolymers & Soft MatterInterdisciplinary Physics

Authors & Affiliations

David O. López1, Josep Salud1, María Rosario de la Fuente2, Nerea Sebastián3, and Sergio Diez-Berart1,*

  • 1Grup de Propietas Físiques dels Materials (GRPFM), Departament de Física, E.T.S.E.I.B. Universitat Politècnica de Catalunya, Diagonal 647, E- 08028 Barcelona, Spain
  • 2Departamento de Física Aplicada II, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apartado 644, E-48080 Bilbao, Spain
  • 3Jožef Stefan Institute, Jamova cesta 39, SI-1000 Ljubljana, Slovenia

  • *sergio.diez@upc.edu

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Vol. 97, Iss. 1 — January 2018

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