Affiliation:
1. TU Darmstadt, Institute of Condensed Matter Physics, 64289 Darmstadt, Germany
Abstract
The intensity of light scattered by liquids has been studied for over a century since the valuable microscopic information about the molecules can be obtained, such as the anisotropy of the molecular polarizability tensor or preferred orientations of neighboring molecules. However, in modern dynamic light scattering experiments, the scattering intensity is usually disregarded, unlike in dielectric spectroscopy, which can be considered as a complementary experimental method, where the dielectric strength is routinely evaluated. The reason lies partly on the fact that the exact form of the equations relating the macroscopically measured light scattering intensity to the microscopic properties of the molecules is debated in the literature. Therefore, as a first step, we compare anisotropy parameters from the literature, calculated from light scattering intensities using different equations, with quantum chemical calculations for over 150 medium-sized molecules. This allows us to identify a consistent form of equations. In a second part, we turn to the depolarized light scattering spectra of 13 van der Waals liquids and some mixtures thereof, recorded with a combination of Tandem–Fabry–Perót and Raman spectroscopies, giving direct access to the reorientational dynamics of the molecules. We discuss how the strength of the structural α-relaxation is connected to the anisotropy parameter, what implication this has for the shape of the α-relaxation, how the components of a mixture—also for the case of ionic liquids—can be identified in this way, and how orientational correlation parameters can be extracted. Additionally, we point out for the example of n-alkanes that for highly flexible molecules, the reorientational motion might not be the decisive source of the depolarized scattered light. We also show that light scattering might serve as a sensitive tool to check the accuracy of a conformer ensemble obtained by quantum chemical calculations.
Funder
Deutsche Forschungsgemeinschaft
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy
Cited by
2 articles.
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