ROTATIONAL SPECTRA AND STRUCTURES OF SMALL CLUSTERS: $Ar_{2}-HCl$ and $Ar_{3}-HCl^{\ast}$

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1986

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Ohio State University

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Microwave rotational spectra have been observed for the small clusters Ar2H35Cl/37Cl and Ar3H35Cl/37Cl. The hyperfine structure of the transitions has been analyzed and the chlorine quadrupole coupling and the line centersdetermined. The line centers were used to obtain the ground state rotational costants. The trimeric cluster, Ar2HCl, has an equilibrium, T-shaped structure with the H pointed at the Ar2m dpoint. The values of A, B. and C determined for the 35cl species with the kirchoff program1 are 1 733,857, 1 667,932, and 844.492 Mhz: τaaaa, τbbbb, τaabb and τabab are -120, -80, 41, and -65 KHz. The quadrupole coupling constants Xaa and XbbXcc are -28.11 and -3. 18 MHz. A value of 3.828 A is found for the Ar-Ar interatomic distance. The Ar3HCl is a symmetric top with the H of the HCl pointing towards the Ar3. The spectroscopic constants for the 35cl version are Bo=843.897 MHz. Dj=2.33KHzDjk=1.82KHz, and Xaa=30.006 MHz. By combining Bo for the H37cl complex (825.981 MHz) with that for H35Cl, We find the Ar-Ar distance in Ar3 to be 3.852 A. Several aspects of the results will be considered; The longer Ar-Ar distance in Ar3 than in Ar2. A comparison of results for the HF and HCl containing clusters. The dependence of the average torsional angle for the HX upon size of the Arn(n=1,2,3), as determined from the hyperfine interactions. Use of the centrifugal distortion to obtain some insight concerning the weak van der waals interactions and vibrational modes.

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Work supported by NSF and PRF. 1 W. H. Kirchoff, J. Mol., Spctros. 41, 333 (1972). Address: Noyes Chemical Laboratory, University of Illinois, Ubrana, IL 61801.

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