Resonant two-photon ionization spectroscopy of jet-cooled OsC

Abstract

The optical spectrum of diatomic OsC has been investigated for the first time, with transitions recorded in the range from 17 390 to 22 990 cm(-1). Six bands were rotationally resolved and analyzed to obtain ground and excited state rotational constants and bond lengths. Spectra for six OsC isotopomers, 192 Os 12C (40.3% natural abundance), 190 Os 12C(26.0%), 189 Os 12C(16.0%), 188 Os 12C(13.1%), 187 Os 12C(1.9%), and 186 Os 12C(1.6%), were recorded and rotationally analyzed. The ground state was found to be X 3 Delta 3, deriving from the 4 delta 3 16 sigma 1 electronic configuration. Four bands were found to originate from the X 3 Delta 3 ground state, giving B 0"=0.533 492(33) cm(-1) and r 0 "=1.672 67(5) A for the 192 Os 12C isotopomer (1 sigma error limits); two of these, the 0-0[19.1]2<--X 3 Delta 3 and 1-0[19.1]2<--X 3 Delta 3 bands, form a vibrational progression with Delta G' 1/2=953.019 cm(-1). The remaining two bands were identified as originating from an Omega"=0 level that remains populated in the supersonic expansion. This level is assigned as the low-lying A 3 Sigma 0+ (-) state, which derives from the 4 delta 2 16 sigma 2 electronic configuration. The OsC molecule differs from the isovalent RuC molecule in having an X 3 Delta 3 ground state, rather than the X 2 delta 4, 1 Sigma+ ground state found in RuC. This difference in electronic structure is due to the relativistic stabilization of the 6s orbital in Os, an effect which favors occupation of the 6s-like 16 sigma orbital. The relativistic stabilization of the 16 sigma orbital also lowers the energy of the 4 delta 2 16 sigma 2, 3 Sigma(-) term, allowing this term to remain populated in the supersonically cooled molecular beam.