IMPROVED ANALYSES OF INFRARED AND VISIBLE EMISSION SPECTRA OF THE $H_{3}$ AND $D_{3}$ MOLECULES

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2002

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Ohio State University

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Electronic emission spectra of the neutral $H_{3}$ and $D_{3}$ molecules obtained with a $Droege-Engelking^{a}$ corona discharge source were described at a previous $symposium.^{b}$ The present work is concerned with analyses of these data for the complex of 3d, 3s, and $3p_{0}$ upper states, where the symbols mean $nl_{\lambda}$. The lower states are $3p_{1}$ (for the infrared) and $2p_{0}$ (for the visible). In $H_{3}$ a ($3s, 3d_{0}$) perturbation is recognised, in addition to the ($3p_{0}, 3d_{1}$) perturbation discussed $previously.^{c}$ The decreased interference by $H_{2}$ or $D_{2}$ in these spectra has made it possible to improve the lower-state combination differences and constants. However, the standard deviations in the fits of the upper states of both $H_{3}$ and $D_{3}$ are still quite large. This is possibly due to numerous small perturbations by background states. It would also be desirable to replace the present effective Hamiltonians by a variational-type treatment of centrifugal effects.

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$^{a}$A. T. Droege and P. C. Engelking, Chem. Phys. Lett. 96, 316 (1983). $^{b}$Paper TA 12 (1991). $^{c}$G. Herzberg, J. T. Hougen, and J. K. G. Watson, Can. J. Phys. 60, 1261 (1982)
Author Institution: Laboratoire de Photophysique Mol\'eculaire du CNRS, B\^{a}timent 350, Universit\'e de Paris-Sud; Steacie Institute for Molecular Sciences, National Research Council of Canada

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