NEW RYDBERG-RYDBERG TRANSITIONS OF THE ArH AND ArD MOLECULES: BANDS INVOLVING THE $4f$ COMPLEX OF ArD
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Date
1995
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Ohio State University
Abstract
The $4f \rightarrow 5s$ transition of ArD is observed in $Ar/D_{2}$ discharges as a band near $4830 {\AA}^{1} (\nu_{00} = 20682 cm^{-1})$ with O, Q and S-form branches. On the basis of a preliminary rotational analysis of this band, the transitions $4f \rightarrow 3d\sigma, 4f \rightarrow 3d\pi$, and $4f \rightarrow 3d\delta$ to the three $components^{2-4}$ of the 3d complex could be assigned to bands at 4371, 7666 and $6045 cm^{-1}$, respectively. These bands give information on components of the 4f complex not seen in the $4f \rightarrow 5s$ band. The 4f complex is found to be a good example of Hund's case (d), with R = 0 splittings that are predominantly of second-rank tensor type with the coefficient of $\lambda^{2}$ equal to $16.5 cm^{-1}$. A number of small perturbations are probably due to vibrational levels of other electronic states, but two larger perturbations near R = 11 and R = 24 are attributed to v = 0 of the $4d\delta$ and $4d\sigma$ states, respectively. The quantum defects of the 4f and other states will be discussed in terms of the properties of the $ArH^{+}$ or $ArD^{+}$ core, including the l-mixing effects of the core electric dipole $moment^{5}$.
Description
$^{1}$ R. H. Lipson, Mol. Phys. 65, 1217-1225 (1988). $^{2}$ J. W. C. Johns, J. Mol. Spectrosc. 36, 488-510 (1970). $^{3}$ I. Dabrowski, G. DiLonardo, G. Herzberg, J. W. C. Johns, D. A. Sadovskii, and M. Vervloet, J. Chem. Phys. 97, 7093-7110 (1992). $^{4}$ I. Dabrowski, D. Tokaryk, M. Vervloet, and J. K. G. Watson, previous paper. $^{5}$ J. K. G. Watson, Mol. Phys. 81, 277-289 (1994).
Author Institution: National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.; University of Western Ontario, London, Ontario, Canada N6A 5B7
Author Institution: National Research Council of Canada, Ottawa, Ontario, Canada K1A 0R6.; University of Western Ontario, London, Ontario, Canada N6A 5B7