Abstract

The gas phase infrared spectrum of monoisotopic H 3Si 37Cl has been reinvestigated in the ν 1/ ν 4 region near 2200 cm −1, using a Fourier transform spectrometer, with a nominal resolution of 0.0027 cm −1. The rovibrational analysis confirms, besides the weak Coriolis x, y resonance between the ( v 1 = 1) and ( v 4 = 1) levels, the existence of two strong local perturbations in the ν 4 band. These are caused by rotational (Δ k = Δ l = ±1) type resonances with ν 3 + ν 5 ± 1 + ν 6 ∓ 1 and ν 3 + ν 5 ∓ 1 + ν 6 ∓ 1 , respectively. Another local perturbation of the 12 ⩽ KΔ K ⩽ 14 subbands of the ν 4 band, probably due to a (Δ k = Δ l = ±1) interaction with ν 2 + 2 ν 6 0 , was detected and analyzed. All these local perturbations have been studied individually using a simple model of two interacting sublevels. Without the transitions involved in the local perturbations, more than 2000 lines of the ν 1/ ν 4 band system were used to obtain a complete set of vibration–rotation parameters set for the v 1 = 1 and v 4 = 1 states. By means of a band contour simulation, both the transition moment ratio ∣ M 4: M 1∣ = 1.25 and a positive sign of the Coriolis intensity perturbation were determined. The present results, together with the accurate existing data for ν 2, ν 3, ν 5, and ν 6 bands, allowed us to derive the experimental values, A e = 2.8722945(37) cm −1 and B e = 0.2182248(22) cm −1, which are compared with those of ab initio calculations.

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