15min:
THE MILLIMETER/SUBMILLIMETER SPECTRUM OF BaSH(X2A'): EVEN FURTHER INVESTIGATIONS OF THE METAL-SULFUR BOND.

A. JANCZYK AND L. M. ZIURYS, Department of Chemistry, Department of Astronomy, and Steward Observatory, University of Arizona, Tucson, AZ 85721.

The pure rotational spectrum of BaSH (X2A') and one of its isotopomers, BaSD, were recorded using millimeter/submillimeter wave direct absorption techniques in the range 320-364 GHz. This radical was produced by reacting barium vapor with H2S in the presence of a d.c. discharge. Ten transitions, ranging from J=66 rightarrow 67 to 75 rightarrow 76, were measured for BaSH, as well as 5 transitions for the deuterium isotopomer. The spectra exhibit complex Ka ladder structure for both molecules, consistent with a bent geometry. Spin- rotation splittings of approximately 54 MHz were also observed in every transition. Rotational and fine structure constants have been determined for both isotopomers, as well as an r0 structure for BaSH. This study shows that barium hydrosulfide is bent with an angle of Theta = 88\circ, and therefore is significantly different from linear BaOH. This structural change indicates more covalent bonding character in the BaSH, relative to its hydroxide analog.