Relation between macroscopic and microscopic dielectric relaxation times in water dynamics

Vladimir I. Arkhipov, Noam Agmon*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

A simplified derivation for the ratio of macroscopic to microscopic relaxation times of polar liquids is based on the Mori-Zwanzig projection-operator technique, with added statistical assumptions. We obtain several useful forms for the lifetime ratio, which we apply to the dynamics of liquid water. Our theoretical single-molecule relaxation times agree with the second Debye relaxation times as measured by frequency-domain dielectric spectroscopy of water and alcohols. From the theory, fast relaxation modes couple to the Debye relaxation time, τD, through very large water clusters, and their temperature dependence is similar to that of τD. Slower modes are localized to smaller water clusters and exhibit weaker temperature dependence. This is exemplified by the lifetime ratios measured by time-domain dielectric spectroscopy and optical Kerr effect spectroscopy, respectively.

Original languageEnglish
Pages (from-to)363-371
Number of pages9
JournalIsrael Journal of Chemistry
Volume43
Issue number3-4
DOIs
StatePublished - 2003

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