Solvation dynamics and the dielectric response in a glass-forming solvent: from picoseconds to seconds

R. Richert, F. Stickel, R. S. Fee, M. Maroncelli

Research output: Contribution to journalArticle

91 Citations (Scopus)

Abstract

We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}/ε{lunate}s) 1 2.

Original languageEnglish (US)
Pages (from-to)302-308
Number of pages7
JournalChemical Physics Letters
Volume229
Issue number3
DOIs
StatePublished - Oct 28 1994

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Solvation
solvation
Glass
glass
Dielectric relaxation
Polymethyl Methacrylate
dielectric polarization
Relaxation time
Melting point
Glass transition
decay
Viscosity
Polarization
melting points
monitors
coverings
relaxation time
viscosity
shift
curves

All Science Journal Classification (ASJC) codes

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

Cite this

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abstract = "We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}∞/ε{lunate}s) 1 2.",
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Solvation dynamics and the dielectric response in a glass-forming solvent : from picoseconds to seconds. / Richert, R.; Stickel, F.; Fee, R. S.; Maroncelli, M.

In: Chemical Physics Letters, Vol. 229, No. 3, 28.10.1994, p. 302-308.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Solvation dynamics and the dielectric response in a glass-forming solvent

T2 - from picoseconds to seconds

AU - Richert, R.

AU - Stickel, F.

AU - Fee, R. S.

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N2 - We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}∞/ε{lunate}s) 1 2.

AB - We have measured the response times of sol vation dynamics in the range 100 ps to 100 s and the dielectric relaxation covering 10 decades in frequency for the glass-forming solvent 2-methyltetrahydrofuran. In this wide range of solvent viscosities, from the glass transition to beyond the melting point, the mean relaxation times for the two techniques which monitor dipolar orientation are identical within our resolution. For two characteristic decay traces recorded on the time scales of 10 ns and 1 s we compare the observed Stokes-shift dynamics with various theoretical approaches. The decay pattern is reproduced by the dipolar dynamic-mean-spherical-approximation, whereas the absolute time scale of the solvation is mapped by the dielectric polarization itself. For the solvent under study we find almost perfect agreement between experiment and the dipolar dMSA theory if the time scale of the predicted curve is rescaled by a factor of (ε{lunate}∞/ε{lunate}s) 1 2.

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