Observation and analysis of the ν2 and ν3 fundamental bands of the H2D+ ion

Abstract

The observation of the high-resolution absorption spectrum of the H2D+ molecular ion in the region 2010–2610 cm−1 in discharges through mixtures of H2 and D2 gases is reported. Two types of tunable monochromatic sources are employed, either a diode laser (in Ottawa) or a difference-frequency laser system (in Chicago), and the sensitivity is improved by using either discharge modulation or Doppler velocity modulation techniques. A total of 66 new lines of H2D+ have been measured and assigned, mostly on the basis of ground-state combination differences, to specific rotational transitions of the ν2 and ν3 bands. These data, as well as the two known microwave lines, are fitted by means of two theoretical models, either an effective Hamiltonian model including a Padé representation of a conventional A-reduced centrifugal Hamiltonian for each vibrational level together with Coriolis and higher rotational interactions between ν2 and ν3, or a supermatrix model in which the matrix of the untransformed Hamiltonian is set up in a large vibration-rotation basis and diagonalized directly. In the supermatrix model most of the vibrationally off-diagonal matrix elements are constrained to values derived from Carney’s ab initio calculations, while the ν1 parameters are fitted to the observed lines of Amano. Because of the large number of parameters required in the effective Hamiltonian, the less flexible supermatrix model was valuable as a check of the assignments. The results of these fits make it possible to assign seven of the nine lines reported by Shy, Farley, and Wing in 1981. The observed band origins, ν2=2205.87 cm−1 and ν3=2335.45 cm−1, as well as the rotational constants, are in good agreement with ab initio predictions. With the use of one calculated term value to relate the stacks of levels with even and odd values of K″a, a table of observed term values of the lower rotational levels of the ground state and the ν2 and ν3 states is constructed.