Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues
Article first published online: 22 APR 2013
Copyright © 2013 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Volume 44, Issue 6, pages 857–865, June 2013
How to Cite
James, T. M., Schlösser, M., Fischer, S., Sturm, M., Bornschein, B., Lewis, R. J. and Telle, H. H. (2013), Accurate depolarization ratio measurements for all diatomic hydrogen isotopologues. J. Raman Spectrosc., 44: 857–865. doi: 10.1002/jrs.4283
- Issue published online: 5 JUN 2013
- Article first published online: 22 APR 2013
- Manuscript Accepted: 4 FEB 2013
- Manuscript Revised: 29 JAN 2013
- Manuscript Received: 17 DEC 2012
- hydrogen isotopologues;
- Raman depolarization ratio
The Raman depolarization ratios for individual Q1(J”) branch lines of all diatomic hydrogen isotopologues – H2, HD, D2, HT, DT, and T2 – were measured, for all rotational levels with population larger than 1/100 relative to the Boltzmann maximum at room temperature. For these measurements, the experimental setup normally used for the monitoring of the tritiated hydrogen molecules at KArlsruhe TRItium Neutrino experiment was adapted to optimally control the excitation laser power and polarization, and to precisely define the Raman light collection geometry. The measured Raman depolarization values were compared to theoretical values, which are linked to polarizability tensor quantities. For this, the ‘raw data’ were corrected taking into account distinct aspects affecting Raman depolarization data, including (1) excitation polarization impurities; (2) extended Raman excitation volumes; and (3) Raman light collection over finite solid angles. Our corrected depolarization ratios of the hydrogen isotopologues agree with the theoretical values (based on ab initio quantum calculations by R.J. LeRoy, University of Waterloo, Canada) to better than 5% for nearly all of the measured Q1(J”) lines, with 1σ confidence level. The results demonstrate that reliable, accurate Raman depolarization ratios can be extracted from experimental measurements, which may be substantially distorted by excitation polarization impurities and by geometrical effects. Copyright © 2013 John Wiley & Sons, Ltd.