Subpicosecond resolution studies of solvation dynamics in polar aprotic and alcohol solvents

Edward W. Castner, Mark Maroncelli, Graham R. Fleming

Research output: Contribution to journalArticle

294 Citations (Scopus)

Abstract

Subpicosecond resolution measurements of the kinetics of dipolar solvation have been made. The time resolved Stokes shift of a dye molecule, LDS-750 was measured using the fluorescence upconversion technique in the solvents acetonitrile, DMSO, nitrobenzene, methanol, and n-butanol. The solvation dynamics in both aprotic and alcohol solvents occur on a time scale roughly given by the longitudinal relaxation time as predicted by simple continuum theories. The relaxation in nitrobenzene and butanol is nonexponential and the relaxation in methanol is significantly faster than the calculated time. These deviations from simple theory are discussed in the context of (i) the significance of high frequency dispersions in the dielectric response, (ii) translational contributions to the solvent relaxation, and (iii) molecular aspects of the solvation not accounted in the continuum description.

Original languageEnglish (US)
Pages (from-to)1090-1097
Number of pages8
JournalThe Journal of Chemical Physics
Volume86
Issue number3
DOIs
StatePublished - Jan 1 1987

Fingerprint

Solvation
solvation
alcohols
nitrobenzenes
Alcohols
Methanol
methyl alcohol
continuums
Butanols
1-Butanol
Dimethyl Sulfoxide
Dispersions
Relaxation time
acetonitrile
Coloring Agents
relaxation time
dyes
Fluorescence
deviation
fluorescence

All Science Journal Classification (ASJC) codes

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

Cite this

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Subpicosecond resolution studies of solvation dynamics in polar aprotic and alcohol solvents. / Castner, Edward W.; Maroncelli, Mark; Fleming, Graham R.

In: The Journal of Chemical Physics, Vol. 86, No. 3, 01.01.1987, p. 1090-1097.

Research output: Contribution to journalArticle

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