High-resolution spectroscopy of HCl and DCl isolated in solid parahydrogen: Direct, induced, and cooperative infrared transitions in a molecular quantum solid
- 8 January 2002
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 116 (2), 594-607
- https://doi.org/10.1063/1.1421066
Abstract
The infrared spectroscopy and rovibrational dynamics of HCl and DCl dopants in solid parahydrogen were investigated using high-resolution spectroscopic methods. The absorption spectra of HCl and DCl monomers in solid closely resemble the corresponding low temperature gas phase spectra, indicating that the gas phase vibrational and rotational quantum numbers of the dopant are conserved within the solid. Small deviations from gas phase behavior are observed, however, such as a reduced HCl rotational energy level spacing and splitting of the fivefold orientational degeneracy of HCl rotational states with In addition, the pure vibrational transition, which is infrared inactive in pure solid is detected in the HCl doped sample. We propose that this transition is induced in molecules by neighboring HCl molecules through a weak “overlap induction” mechanism that is the only induction mechanism operative for impurities in Rovibrational transitions are also detected near the induced absorption; these are attributed to cooperative transitions involving single photon excitation of pairs. Detailed isotopic analysis reveals that these cooperative transitions involve pure vibrational excitation of the and pure rotational excitation of the HCl. Two-molecule transitions have long been studied for isotopic and rotational dopants (e.g., HD, orthohydrogen) in solid but this is the first time such cooperative transitions have been attributed to a chemical impurity in matrices.
Keywords
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