Confinement for More Space: A Larger Free Volume and Enhanced Glassy Dynamics of 2-Ethyl-1-hexanol in Nanopores

J Phys Chem Lett. 2015 Sep 17;6(18):3708-12. doi: 10.1021/acs.jpclett.5b01533. Epub 2015 Sep 4.

Abstract

Broadband dielectric spectroscopy and positron annihilation lifetime spectroscopy are employed to study the molecular dynamics and effective free volume of 2-ethyl-1-hexanol (2E1H) in the bulk state and when confined in unidirectional nanopores with average diameters of 4, 6, and 8 nm. Enhanced α-relaxations with decreasing pore diameters closer to the calorimetric glass-transition temperature (T(g)) correlate with the increase in the effective free volume. This indicates that the glassy dynamics of 2D constrained 2E1H is mainly controlled by density variation.

Keywords: Debye process; confinement; free volume; nanopores; structural relaxation.

Publication types

  • Research Support, Non-U.S. Gov't