Spectroscopic line shapes in polar supercooled liquids

Ranko Richert, Achim Wagener

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

We have measured the inhomogeneously broadened T1 → S0 (0-0) emission spectra of quinoxaline in a series of organic glass-forming solvents, which are characterized in terms of their optical and static dielectric constants. The experimental results regarding Stokes shift and inhomogeneous line width are compared with the predictions of a statistical mechanical line shape theory (Loring, R. F. J. Phys. Chem. 1990, 94, 513), whose relevant input parameters are known. Using the MSA approach for delineating the solvation free energy, a good agreement between prediction and observation is achieved, indicating of a clear improvement over Onsager's continuum calculation. As a conclusion, spectroscopic line shapes in these systems are completely determined by electrostatic interaction and, therefore, can be rationalized quantitatively in terms of the solvent dielectric constant. The relation to empirical polarity scales is briefly discussed.

Original languageEnglish (US)
Pages (from-to)3146-3150
Number of pages5
JournalJournal of Physical Chemistry
Volume97
Issue number13
StatePublished - 1993
Externally publishedYes

Fingerprint

line shape
Permittivity
permittivity
quinoxalines
Quinoxalines
Solvation
Liquids
liquids
predictions
Coulomb interactions
Linewidth
Free energy
solvation
polarity
emission spectra
free energy
electrostatics
continuums
Glass
glass

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Spectroscopic line shapes in polar supercooled liquids. / Richert, Ranko; Wagener, Achim.

In: Journal of Physical Chemistry, Vol. 97, No. 13, 1993, p. 3146-3150.

Research output: Contribution to journalArticle

Richert, Ranko ; Wagener, Achim. / Spectroscopic line shapes in polar supercooled liquids. In: Journal of Physical Chemistry. 1993 ; Vol. 97, No. 13. pp. 3146-3150.
@article{26182b6f7bf84e6da51bcab7b6d30c23,
title = "Spectroscopic line shapes in polar supercooled liquids",
abstract = "We have measured the inhomogeneously broadened T1 → S0 (0-0) emission spectra of quinoxaline in a series of organic glass-forming solvents, which are characterized in terms of their optical and static dielectric constants. The experimental results regarding Stokes shift and inhomogeneous line width are compared with the predictions of a statistical mechanical line shape theory (Loring, R. F. J. Phys. Chem. 1990, 94, 513), whose relevant input parameters are known. Using the MSA approach for delineating the solvation free energy, a good agreement between prediction and observation is achieved, indicating of a clear improvement over Onsager's continuum calculation. As a conclusion, spectroscopic line shapes in these systems are completely determined by electrostatic interaction and, therefore, can be rationalized quantitatively in terms of the solvent dielectric constant. The relation to empirical polarity scales is briefly discussed.",
author = "Ranko Richert and Achim Wagener",
year = "1993",
language = "English (US)",
volume = "97",
pages = "3146--3150",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Spectroscopic line shapes in polar supercooled liquids

AU - Richert, Ranko

AU - Wagener, Achim

PY - 1993

Y1 - 1993

N2 - We have measured the inhomogeneously broadened T1 → S0 (0-0) emission spectra of quinoxaline in a series of organic glass-forming solvents, which are characterized in terms of their optical and static dielectric constants. The experimental results regarding Stokes shift and inhomogeneous line width are compared with the predictions of a statistical mechanical line shape theory (Loring, R. F. J. Phys. Chem. 1990, 94, 513), whose relevant input parameters are known. Using the MSA approach for delineating the solvation free energy, a good agreement between prediction and observation is achieved, indicating of a clear improvement over Onsager's continuum calculation. As a conclusion, spectroscopic line shapes in these systems are completely determined by electrostatic interaction and, therefore, can be rationalized quantitatively in terms of the solvent dielectric constant. The relation to empirical polarity scales is briefly discussed.

AB - We have measured the inhomogeneously broadened T1 → S0 (0-0) emission spectra of quinoxaline in a series of organic glass-forming solvents, which are characterized in terms of their optical and static dielectric constants. The experimental results regarding Stokes shift and inhomogeneous line width are compared with the predictions of a statistical mechanical line shape theory (Loring, R. F. J. Phys. Chem. 1990, 94, 513), whose relevant input parameters are known. Using the MSA approach for delineating the solvation free energy, a good agreement between prediction and observation is achieved, indicating of a clear improvement over Onsager's continuum calculation. As a conclusion, spectroscopic line shapes in these systems are completely determined by electrostatic interaction and, therefore, can be rationalized quantitatively in terms of the solvent dielectric constant. The relation to empirical polarity scales is briefly discussed.

UR - http://www.scopus.com/inward/record.url?scp=0042167910&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0042167910&partnerID=8YFLogxK

M3 - Article

VL - 97

SP - 3146

EP - 3150

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 13

ER -