NEW RYDBERG-RYDBERG TRANSITIONS OF THE ArH AND ArD MOLECULES: BANDS INVOLVING s, p AND d -ELECTRONIC STATES
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Date
1995
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Publisher
Ohio State University
Abstract
The previous $analyses^{1-3}$ of the spectra of ArH and ArD are extended to other transitions between s, p and d complexes, using a case (d) Hamiltonian in which the rotational and centrifugal energies are expressed in powers of $R^{2}$. While I is not a perfect quantum number, it provides convenient labels for the states. The present analysis of bands involving the lowest bound state (5s) is restricted to ArD because the corresponding state of ArH is strongly $predissociated^{1}$. The bands $5p \rightarrow 5s$ and $6p \rightarrow 5s$ have been observed, but analysis of the former is hampered by interference by $D_{3}$ emission. These bands show that the small $\sigma-\pi$ separation found in the 4p $complex^{3}$ is accidental. For example, $6p\sigma - 6p\pi$ is $69.9 cm^{-1}$ (from the R = 0 Hamiltonian), whereas the corresponding separation in 4p is $2.0 cm^{-1}$. Observation of the $3 d \delta \rightarrow 4p$ band completes the 3d complex, whose wide splitting ($\sigma, \pi$ and $\delta$ components at 16311, 13016, and $14637 cm^{-1}$ relative to 5s in ArD) corresponds to an almost pure fourth-rank tensor pattern. The bands $6s \rightarrow 4p$ and $8s \rightarrow 4p$ have also been analysed.
Description
$^{1}$ J. W. C. Johns, J. Mol. Spectrosc. 36, 488-510 (1970). $^{2}$ R. H. Lipson, Mol. Phys. 65, 1217-1225 (1988). $^{3}$ I. Dabrowski, G. DiLonardo, G. Herzberg, J. W. C. Johns, D. A. Sadovskii, and M. Vervloet, J. Chem. Phys. 97, 7093-7110 (1992).
Author Institution: National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.; Université de Paris-Sud, 91405 Orsay, France
Author Institution: National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.; Université de Paris-Sud, 91405 Orsay, France