High-resolution Fourier transform spectra and rotational analysis of monoisotopic H 374Ge 35Cl and H 374Ge 37Cl in the ν2/ ν5/2 ν3 region near 850 cm -1
Abstract
The gas phase infrared spectra of the monoisotopic germyl chloride species H 374Ge 35Cl (7435) and H 374Ge 37Cl (7437) in the ν2/ ν5/2 ν3 region near 850 cm -1 have been studied with a resolution (fwhm) of ca. 0.002 cm -1 employing a Fourier transform spectrometer. A total of 4628 and 3461 transitions of (7435) and (7437), respectively, have been assigned with Kmax = 15 and Jmax = 80 for ν2( a1) and ν5( e). For 2 ν3 of (7435), Kmax and Jmax were 6 and 61, respectively. Precise J-dependent ground state constants up to sextic coefficients have been determined from a fit (σ ⋍ 1.3 × 10 -4 cm -1) of 1635 and 751 combination differences for (7435) and (7437), respectively. One pair of excited state levels split by Δ l = ±1, Δk = ⊣2 interactions has been observed, and A0 (in connection with DK0 determined previously) of (7437) has been obtained from the related normal and perturbation-allowed transitions. Strong Coriolis interaction, |ζ 2,5i| ⋍ 0.65 , i = x, y, with positive intensity perturbation occurs between ν2( a1) and ν5( e). For (7437), the perturbation by 2 ν3( A1) is local and restricted to the ( kl) = -8 sublevels of ν5. In contrast, ν2 and 2 ν3 are sufficiently close in (7435) that extended Fermi interactions, | W233F| = 1.27 cm -1, negative intensity perturbation, become dominant. The observed transitions have been fitted, σ ⋍ 1.3 × 10 -4 cm -1, to excited state parameters, and a model taking into account Fermi, Δ l = Δ k = ±1, Δ l = Δ k = ±2 and Δ l = ±1, Δk = ⊣2 interactions has been employed. The following rounded vibrational frequencies ( {7435}/{7437}) have been determined: ν20, {847.650}/{847.456}, ν50, {873.844}/{873.833}, and 2 ν30, {843.070}/{827.607}cm-1.
- Publication:
-
Journal of Molecular Spectroscopy
- Pub Date:
- March 1986
- DOI:
- 10.1016/0022-2852(86)90264-X
- Bibcode:
- 1986JMoSp.116..228B