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

Ed Castner, Mark Maroncelli, Graham R. Fleming

Research output: Contribution to journalArticle

289 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
Pages (from-to)1090-1097
Number of pages8
JournalJournal of Chemical Physics
Volume86
Issue number3
Publication statusPublished - 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

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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

In: Journal of Chemical Physics, Vol. 86, No. 3, 1987, p. 1090-1097.

Research output: Contribution to journalArticle

Castner, Ed ; Maroncelli, Mark ; Fleming, Graham R. / Subpicosecond resolution studies of solvation dynamics in polar aprotic and alcohol solvents. In: Journal of Chemical Physics. 1987 ; Vol. 86, No. 3. pp. 1090-1097.
@article{64e827ad1ecc4f9e94a6f9edeefb1653,
title = "Subpicosecond resolution studies of solvation dynamics in polar aprotic and alcohol solvents",
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.",
author = "Ed Castner and Mark Maroncelli and Fleming, {Graham R.}",
year = "1987",
language = "English",
volume = "86",
pages = "1090--1097",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "3",

}

TY - JOUR

T1 - Subpicosecond resolution studies of solvation dynamics in polar aprotic and alcohol solvents

AU - Castner, Ed

AU - Maroncelli, Mark

AU - Fleming, Graham R.

PY - 1987

Y1 - 1987

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=33845487668&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845487668&partnerID=8YFLogxK

M3 - Article

VL - 86

SP - 1090

EP - 1097

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

ER -