Infrared and near infrared emission spectra of SbH and SbD

The X3Σ− ground state vibration-rotation spectrum of SbH and the near infrared spectra of the b1Σ+-X3Σ− transitions of SbH and SbD have been measured at high resolution by Fourier transform spectroscopy. The SbH and SbD radicals were generated in a tube furnace with a D.C. discharge of a flowing mixture of argon, hydrogen (or deuterium), and antimony vapor. In the infrared region, the 1-0 and 2-1 bands of the three components (0+, 1e, and 1f) as well as the 0+ component of the 3-2 band were observed for 121SbH and 123SbH. In the near infrared region, the 0-0, 1-1, and 2-2 bands of the b1Σ+-X3Σ− system of both SbH and SbD as well as the 3-3 band of SbD were observed. Except for a few lines, the antimony isotopic shift was not resolved for these electronic spectra. The present data set was combined with the available ground state data on SbD and a1Δ data for SbH and SbD from previous work, and a least-squares fit was performed for each of the four isotopologues: 121SbH, 123SbH, 121SbD, and 123SbD. Improved spectroscopic constants were obtained for the observed vibrational levels of the X3Σ−, a1Δ, and b1Σ+ states of these four isotopologues. In addition, all the above data were also fitted simultaneously to a multi-isotopologue Dunham model, which yielded Dunham constants and Born-Oppenheimer breakdown parameters for these three electronic states. Interestingly, we found that Born-Oppenheimer breakdown corrections were also required for some of the spin-spin and spin-rotation parameters of the X3Σ− state.