Open AccessStrong increase of correlations in liquid glycerol observed by nonlinear dielectric techniques
Author(s) -
Erik Thoms,
Dmitry V. Matyushov,
Ranko Richert
Publication year - 2022
Publication title -
journal of chemical physics online/the journal of chemical physics/journal of chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.071
H-Index - 357
eISSN - 1089-7690
pISSN - 0021-9606
DOI - 10.1063/5.0093235
Subject(s) - dielectric , nonlinear system , saturation (graph theory) , condensed matter physics , dielectric response , limit (mathematics) , thermodynamics , chemistry , materials science , stoichiometry , field (mathematics) , statistical physics , analytical chemistry (journal) , computational physics , physics , mathematics , quantum mechanics , mathematical analysis , optoelectronics , chromatography , combinatorics , pure mathematics
Non-linear dielectric measurements are an important tool to access material properties and dynamics concealed in their linear counterparts, but the available data is 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 non-linear effects in glycerol over a wide temperature range from 230 K 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 V 2 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.