The van der Waals complexes, NeDCl and ArDCl, are produced in a slit jet supersonic expansion and observed via direct absorption of tunable midhyphen;infrared Pbhyphen;salt diode laser radiation. For the NeDCl complex, the DCl stretch fundamental lsqb;ngr;0=2091.3717(4) cmminus;1rsqb; and the DCl Sgr; and Pgr;e,thinsp;fbend combination bands lsqb;ngr;0=2099.5760(4) and 2104.9465(4) cmminus;1, respectivelyrsqb; are observed. The DCl stretch fundamental and Pgr;e,thinsp;fcombination band are observed for ArDCl at 2089.4180(2) and 2117.4443(3) cmminus;1, respectively. The relative fundamental vs bend combination band intensity distributions are very different for the two complexes. The ArDCl fundamental to Pgr; bend combination band intensity ratio is 4:1, whereas for NeDCl the corresponding ratio is 1:8. This anomalous intensity pattern for NeDCl and the proximity of the bend combination bands to the DClR(0) line indicate that the DCl diatomic is exhibiting nearly free rotation within this complex, compared to more restricted librational motion of DCl in ArDCl. Strong Coriolis interactions between Pgr;eand Sgr; bend states are observed for both complexes and analyzed quantitatively for NeDCl. The observed NeDCl and ArDCl absorption linewidths are only slightly larger than the instrumental limit determined from nearby OCS monomer absorptions in the slit jet, but the differences are not of high statistical significance. This FWHM of the observed transitions dictates a rigorous lower limit to the vibrational predissociation lifetime of 3 ns. Experimentally determined rotational constants, vibrational frequencies, and relative intensities are compared to predictions based on existing empirical potential surfaces.
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