Strong increase of correlations in liquid glycerol observed by nonlinear dielectric techniques

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Abstract

Nonlinear dielectric measurements are an important tool to access material properties and dynamics concealed in their linear counterparts, but the available data are often intermittent and, on occasion, even contradictory. Employing and refining a recently developed technique for high ac field dielectric measurements in the static limit, we ascertain nonlinear effects in glycerol over a wide temperature range from 230 to 320 K. We find that the temperature dependence of the Piekara factor a, which quantifies the saturation effect, changes drastically around 290 K, from ∂ a/∂ T = +1.4 to -130 in units of 10-18 V2 m-2 K-1. These high values of |a| quantify not only elevated dielectric saturation effects but also indicate a temperature driven increase in higher-order orientational correlations and considerable correction terms with respect to the central limit theorem. No signature of this feature can be found in the corresponding low field data.

Original languageEnglish (US)
Article number171102
JournalJournal of Chemical Physics
Volume156
Issue number17
DOIs
StatePublished - May 7 2022
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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