Polarization response of a dielectric continuum to a motion of charge

Ranko Richert, Hermann Wagner

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

In cases where dielectric relaxation dominates the time scale of molecular processes which involve the motion of charge (e.g., solvation dynamics, electron transfer reactions, or chemical reactions), the relevant time scale is the longitudinal relaxation time τL, which is generally faster than the dielectric relaxation time τD. Numerical calculations of the polarizations PD(t) with dE(t)/dt = 0 and PE(t) with dD(t)/dt = 0 for an electrical RC network equivalent to an arbitrary dielectric function ε*(ω) are performed in order to generalize the relation between τL and τD which only for the Debye case reads τL = τDεs. The results for non-Debye systems as a function of relaxation time dispersion and relaxation strength are that 〈τL〉 ≪ 〈τD〉εs whereas the decay profiles for PD(t) and PE(t) are similar. The normalized field decay PE(t) represents a continuum model prediction for the Stokes shift correlation function C(t) observed in solvation dynamics experiments.

Original languageEnglish (US)
Pages (from-to)10948-10951
Number of pages4
JournalJournal of Physical Chemistry
Volume99
Issue number27
StatePublished - 1995
Externally publishedYes

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Relaxation time
Dielectric relaxation
relaxation time
Solvation
Polarization
continuums
solvation
polarization
RC circuits
decay
Chemical reactions
chemical reactions
electron transfer
Electrons
shift
profiles
predictions
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Polarization response of a dielectric continuum to a motion of charge. / Richert, Ranko; Wagner, Hermann.

In: Journal of Physical Chemistry, Vol. 99, No. 27, 1995, p. 10948-10951.

Research output: Contribution to journalArticle

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