MEASUREMENT OF THE VIBRATION-ROTATION SPECTRUM OF THE HYDROXIDE ANION ($OH^{-}$) BY VELOCITY MODULATION LASER SPECTROSCOPY
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Date
1986
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Ohio State University
Abstract
Guided by the ab initio predictions for the $OH^{-}$ fundamental made by Lee and Schaefer (1) and by Werner, Rosmus, and Reinsch (2) along with the laser photodetachment results of Schulz et al. (3), we measured the $v_{1\leftarrow 0}$ band of $^{16}OH^{-}$ and $^{18}OH^{-}$ by velocity modulation spectroscopy with a color center laser (4). The $OH^{-}$ concentration was found to be maximized in a $Ar/H_{2}/O_{2}$ or $Ar/H_{2}/H_{2}O$ discharge where the addition of argon both rotationally heats the $OH^{-}$and increases its overall concentration. The $OH^{-}$ signal was also found to be dramatically dependent on the presence of metal sputtered on the discharge cell wall. The $^{16}OH^{-}$ and $^{18}OH^{-}$ bands were analyzed separately with a least squares analysis yielding the equilibrium bond length and vibration-rotation constants through sextic distortion terms. Using the band origins of the two isotopomers, the harmonic vibrational frequencies and first order anharmonicities were calculated.
Description
$^{1}$. T. J. Lee and H. F. Schaefer III, J. Chem. Phys. 83, 1784 (1985). 2. H.-J. Werner, P. Rosmus, and E.-A. Reinsch, J. Chem. Phys. 79, 905 (1983). 3. P.A. Schulz, R.D. Mead, P. L. Jones, and W.C. Lineberger, J. Chem. Phys. 77, 1153 (1982). 4. N.H. Rosenbaum, J. C. Owrutsky, L. M. Tack, and R.J. Saykally, J. Chem. Phys. (accepted). Address of Rosenbaum, Owrutsky, Tack, and Saykally: Department of Chemistry, University of California, Berkeley, CA 94720.
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