The emission spectrum of helium hydride. I. Bands near 8000 Å

Spectra of helium hydride were observed after neutralization of a mass-selected HeH+ beam. The molecules were produced in a fast beam, and so a special setup had to be used to avoid Doppler broadening and a careful calibration procedure had to be applied to determine the line positions and linewidths. In an earlier paper, we reported the first observation of a discrete spectrum of helium hydride, which was discovered by means of an emission band near 8000 Å. In this paper, a detailed analysis of this band for all four stable isotopic mixtures is given. For the deuterides several vibrational bands were observed, which allowed equilibrium molecular constants to be determined. These constants agree with the results of recent ab initio calculations. The similarity of these constants to those of HeH+ in the ground state confirms that the observed states are Rydberg states. Comparison of the molecular constants for different isotopic mixtures shows deviations from the Born–Oppenheimer approximation. Born–Oppenheimer breakdown parameters were derived. Both the upper and lower states show predissociation to the repulsive ground state of helium hydride. The line intensities give evidence of a dependence of the electronic transition moment on the interatomic distance.