The ground-state rotational spectra of five isotopomers (H,S. . .35CI,, H, S. . .35C137CI, H, S. --37C135CI, HDS. . s ~~C I , and D,S-. .35C12) of a complex formed by hydrogen sulfide and chlorine have been observed with a pulsed-nozzle, Fourier-transform microwave spectrometer. The reaction of H , S and CI, was precluded by employing a fast-mixing nozzle. The rotational constant i ( B o + Co), the centrifugal distortion constant D, and the CI-nuclear quadrupole coupling constants xaa(Cli) and xaa(CI0) (i = inner CI atom, o = outer CI atom) were determined in each case. The rotational constants were interpreted, under the assumption of unperturbed monomer geometries, to establish that H, S. . CI, has a geometry in which the SClCl nuclei are collinear or almost collinear, with the CI, subunit nearly perpendicular to the plane of the H, S nuclei. The observed angular geometry is rationalised in terms of a set of rules previously used to discuss hydrogen-bonded complexes B.. -HX. The strength of the interaction, as measured by the force constant k, (determined from D,), and the electric charge redistribution within CI, on formation of H,S -CI, [determined from the xaa(Clx)] both indicate that the complex is of the weak, outer type described by Mulliken. A comparison of the properties of H,S-. CI, and H,S-.-HCI reveals that the complexes are similar in several respects and explanations for these similarities are given in terms of the electric charge distributions of CI, and HCI. In particular, the reason why the angular geometries of both can be predicted by some electrostatically based rules is discussed.
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