A NEW INTERPRETATION OF THE ROTATION AND VIRBATIONAL SPECTRA OF MATRIX-ISOLATED HF.
Loading...
Date
1970
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
Complete spectra of HF and DF in solid solutions of Ne, Ar, Kr, and Xe have been obtained in the vibration-rotation region, supplementing earlier $work.^{1}$. These have been analyzed in conjunction with the pure rotational spectra of the same systems. While these spectra have been $interpreted^{2}$ with the theory of rotation-translation $coupling,^{2}$ good fits require molecular parameters inconsistent with reasonable calculations. The gross features as well as minute details of the spectra are predicted by the theory of polar molecules in liquid solutions, due to D. Robert and L. $Galatry.^{4}$ The important perturbations of the rotational levels arise from potentials of the form $\cos \theta$ and $\cos^{2}\theta$ that can be estimated from molecular parameters. The $\cos\theta$ part is created by the “cell” walls acting on the molecule’s center of interaction which coincides neither with its center of mass nor the center of the cell. The $\cos^{2}\theta$ contribution of due to the anisodropy of the molecular polarizability. This approach accounts for (1) the appearance of a Q line in HF but not in DF, (2) small splittings of the pure rotational lines, and (3) the blue shift of HF lines contrasted to the red shift of DF lines.
Description
This research was supported by the National Science Foundation.
Author Institution: Department of Chemistry, Johns Hopkins University
Author Institution: Department of Chemistry, Johns Hopkins University