Articles you may be interested inA new ab initio intermolecular potential energy surface and predicted rotational spectra of the Ar−H2S complex Theory of depolarized Rayleigh-Brillouin spectra and rotation-translation coupling in molecular liquids and solids Dilute solutions of H2 D2 and HD in liquid argon are studied by examining the 1000-140-cm-1 region of their induced absorption ~pectra. Since the absorption features overlap extensively, an empirical profile analysis is performed. For H2 and D2 several relatively sharp abs~rptions (Llv1/2",,30 cm-I !, which have a Lorentzian line shape and closely correspond to the expected transltlOns of .the freely ro~atmg :olute molecules are observed. The width of these lines appears to be due to uncertamty broadenmg which depends on the time the absorbing solute molecule spends in a particular solvent cavity. Other features, with a 150-cm-1 half-width are fitted with a four-parameter exponential equation and are believed to involve quantized translatio~al energy levels of the solute. The range of translational energy levels, .which is determined by the distribution of solvent cavity sizes, is responsible for their increase? .bandwldths. T~e HD spectrum is unusual in that the rotational selection rules are relaxed and transltlOns corresponding to LlJ = +2, +3, and +4 are observed. Furthermore, all of the rotational absorptio~ fe~ture~ are anomalously broad (LlV1/2"" 50 cm-I ) and their maxima are shifted from the ~as-phase fr:quenc,es III ~n Irregular patte.rn. Because of its asymmetrical mass distribution, rotational motion of HD IS accompamed by a translatIOn of the molecule in its solvent cavity. This rotation-translation interaction has been given quantitative form in a perturbation treatment by Friedmann and Kimel, and the results are consistent with the observed selection rules, frequency shifts, and linewidths in the spectrum of HD in liquid argon.
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