High resolution electronic spectroscopy of the R center dot SH complexes (R=Ne, Ar, Kr)

The high resolution laser induced fluorescence spectra of the (A) over tilde(2) Sigma( )-(X) over tilde(2) Pi(3/2) electronic transition of the R.SH/D (R= Kr, Ar, Ne) van der Waals (vdW) complexes are reported. Analysis of these bands requires the inclusion of rotation, fine and hyperfine structure, spin-rotation interactions, and parity splittings. A number of molecular parameters are determined, along with internuclear bond distances between the R and the SH moiety. Comparison of the present results for R.SH/D is made with the analogous R.OH/D species where applicable. In addition, the detailed ''rotational'' structure and the highly precise determinations of the band origins of the different heavy atom isotopomers are critical for absolute vibrational quantum number assignment in the (A) over tilde state. (C) 1997 American Institute of Physics.