TY - JOUR
T1 - Strong increase of correlations in liquid glycerol observed by nonlinear dielectric techniques
AU - Thoms, Erik
AU - Matyushov, Dmitry V.
AU - Richert, Ranko
N1 - Funding Information:
This research was supported by the National Science Foundation under Grant Nos. DMR-1904601 and CHE-2154465.
Publisher Copyright:
© 2022 Author(s).
PY - 2022/5/7
Y1 - 2022/5/7
N2 - 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.
AB - 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.
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U2 - 10.1063/5.0093235
DO - 10.1063/5.0093235
M3 - Article
C2 - 35525648
AN - SCOPUS:85129479992
SN - 0021-9606
VL - 156
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 17
M1 - 171102
ER -