Multiparticle orientational correlations are responsible for the nonlinear dielectric effect: Analysis of temperature-dependent measurements for glycerol

Research output: Contribution to journalArticlepeer-review

Abstract

The nonlinear dielectric effect (NDE) is traditionally viewed as originating from saturation of the response of individual dipoles in a strong electric field. This mean-field view, mathematically described by the Langevin saturation function, predicts enhanced dielectric saturation at lower temperatures. In contrast, recent experiments for glycerol have shown a sharp increase of the NDE with increasing temperature. The formalism presented here splits the NDE into a sum of a term representing binary correlations of dipolar orientations and terms referring to three- and four-particle orientational correlations. Analysis of experimental data shows that the contribution of three- and four-particle correlations strongly increases at elevated temperatures. The mean-field picture of dielectric saturation as the origin of the NDE is inconsistent with observations. A positive NDE (increment of the field-dependent dielectric constant) is predicted for low-concentration solutions of polar molecules in nonpolar solvents. The dependence of the NDE on the concentration of the polar component is polynomial.

Original languageEnglish (US)
Article number164501
JournalJournal of Chemical Physics
Volume157
Issue number16
DOIs
StatePublished - Oct 28 2022
Externally publishedYes

ASJC Scopus subject areas

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

Fingerprint

Dive into the research topics of 'Multiparticle orientational correlations are responsible for the nonlinear dielectric effect: Analysis of temperature-dependent measurements for glycerol'. Together they form a unique fingerprint.

Cite this