OBSERVATION AND ANALYSIS OF THE ROVIBRATIONAL SPECTRA OF $OCS \cdot \cdot HX (HX = HF, HCl \& HBr)$ DIMERS

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1993

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Ohio State University

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High resolution infrared absorption spectra of the weakly bonded $OCS \cdot \cdot HX$ complexes have been observed in the $2055 cm^{-1}$ region. Infrared spectra of $SCO-HF, SCO-H35Cl, SCO-H^{79}Br$ and $SCO-H^{81}Br$ were obtained on a rapid scan diode laser spectrometer which incorporate a pulsed 12 cm long $\times 200$ micron wide slit nozzle. The spectral features for all three dimers consists of regularly spaced features characteristic of linear hydrogen bonded structures. Ground state rotational constants of SCO-HF and $SCO-H^{35}$Cl agree with previous microwave $measurements.^{1.2}$ It is interesting to note that SCO-HBr complex exhibits a linear structure instead of the bent structure found in $CO_{2}$-HBr and $N_{2}O-HBr$. In addition, the band origin shifts (i.e., $\Delta \nu = \nu_0$ (complex)-$\nu_{0}$(monomer) of the OCS-HX species are quite different from their $CO_{2}$ and $N_{2}O$- $analogs.^{3,4}$ The band origin shifts associated with $CO_{2}$-HX and $N_{2}O$-HX follows the trend $-HF > -HCl > -Br$. In contrast, our infrared results show that the band origin shifts by $-6.8, -7.3, -7.2 cm^{-1}$ for SCO-HF, SCO-HCl and SCO-HBr, respectively.

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$^{1.}$ F.A. Baiocci, T.A. Dixon, C.H. Joyner and W. Klemperer, J. Chem. Phys. 90, 1330 (1989). $^{2.}$E.J. Goodman and A.C. Legon, J. Chem. Soc., Faraday Trans. 2 81, 1709 (1985). $^{3.}$S.W. Sharpe, Y.P. Zeng, C. Wittig and R.A. Beaudet, J. Chem. Phys. 92, 943 (1990). $^{4.}$Y.P. Zeng, S.W. Sharpe, D. Reifschneider, C. Wittig and R.A. Beaudet., J. Chem. Phys. 93, 183 (1990).
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