Journal of Chemical Physics, Vol.116, No.2, 594-607, 2002
High-resolution spectroscopy of HCl and DCl isolated in solid parahydrogen: Direct, induced, and cooperative infrared transitions in a molecular quantum solid
The infrared spectroscopy and rovibrational dynamics of HCl and DCl dopants in solid parahydrogen (pH(2)) were investigated using high-resolution spectroscopic methods. The absorption spectra of HCl and DCl monomers in solid pH(2) 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 pH(2) 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 J=2. In addition, the pure vibrational Q(1)(0) (v=1 <--0, J=0 <--0) H-2 transition, which is infrared inactive in pure solid pH(2), is detected in the HCl doped sample. We propose that this transition is induced in pH(2) molecules by neighboring HCl molecules through a weak "overlap induction" mechanism that is the only induction mechanism operative for J=0 impurities in pH(2). Rovibrational transitions are also detected near the induced Q(1)(0) H-2 absorption; these are attributed to cooperative transitions involving single photon excitation of pH(2)-HCl pairs. Detailed isotopic analysis reveals that these cooperative transitions involve pure vibrational excitation of the pH(2) and pure rotational excitation of the HCl. Two-molecule transitions have long been studied for isotopic and rotational dopants (e.g., D-2, HD, orthohydrogen) in solid pH(2), but this is the first time such cooperative transitions have been attributed to a chemical impurity in pH(2) matrices.