Spectroscopic study of the tunneling dynamics in N₂-water observed in the O-D stretch region

The O-D stretch rovibrational spectra of N₂-D₂O and N₂-DOH were measured and analyzed. A combination band involving the in-plane N₂ bending vibration was also observed. These bands were recorded using a pulsed-slit supersonic jet expansion and a mid-infrared tunable optical parametric oscillator. The spectra were analyzed by considering the feasible tunneling motions, and transitions were fitted to independent asymmetric rotors for each tunneling state. The rotational constants of the four tunneling components of N₂-D₂O were retrieved for the excited vibrational states. A two order of magnitude increase in the tunneling splittings is observed for the asymmetric O-D stretch (ν₃ in D₂O) excitation compared to the symmetric stretch (ν₁ in D₂O) and to the ground vibrational state. This last finding indicates that the ν₃ vibrational state is likely perturbed by a combination state that includes ν₁. Finally, the observation of a local perturbation in the ν₃ vibrational band, affecting the positions of few rovibrational levels, provides an experimental lower limit of the dissociation energy of the complex, D₀ > 120 cm^-1.