THE ANOMALOUS $k=3$ SPLITTINGS OF $PH_{3}$ IN THE $\nu_{2}$ STATE OBSERVED BY RADIOFREQUENCY-INFRARED DOUBLE-RESONANCE
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Date
1987
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Ohio State University
Abstract
We have observed the $k=3$ splittings in the $\nu_{2}$ state of $PH_{3}$ using radiofrequency-infrared double-resonance. The microwave sidebands on $CO_{2}$ laser lines were used as the infrared radiation source. The observed splittings together with those earlier reported by Carlotti $et al.^{1}$ do not agree with the simple $\frac{(J+3)^{*}}{(J-3)^{*}}$ formula, contrary to the similar splittings in the ground state reported by Klemperer and his $colleagues.^{2}$ A more pronounced anomaly has been reported for the $k=6$ and $k=9$ doublings in the $3\nu_{2}$ and $4\nu_{2}$ states of $PH_{3}.{^{3}}$ We explain the anomaly for the $\nu_{2}$ state by taking into account the Coriolis interactions between $\nu_{2} k=3$ levels and various $\nu_{4}k - \ell| = 3n$ levels. The results explain this anomaly well. We have obtained the following splitting parameters for various doublings: \begin{eqnarray*}\Delta_{(\nu_{2},k=3,\ell=0)}& = & 357(40)Hz\\ \Delta_{(\nu_{4},k=2,\ell=-1)} & = & 594(70)kHz\end{eqnarray*}
Description
$^{1}$ M. Carlotti, G. Di Lonardo and A. Trombetti, J. Chem. Phys., 78, 1670 (1983). $^{2}$ P. B. Davies, P. M. Neumann, S. C. Wofsy and W. Klemperer, J. Chem. Phys., 55, 3564 (1971). $^{3}$ P. Bernard and T. Oka, J. Mol. Spectros., 75, 81 (1979)
Author Institution: Department of Chemistry and Department of Astronomy and Astrophysics, The University of Chicago
Author Institution: Department of Chemistry and Department of Astronomy and Astrophysics, The University of Chicago