ROTATIONAL SPECTRA AND STRUCTURE OF $H_{2}S$ COMPLEXES: $Ar(H_{2}S)_{2}$ AND $C_{2}H_{4}-H_{2}S$

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2004

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Ohio State University

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Recently, we determined hydrogen bond radii for HF, HCl, HBr, HI, HCN, $H_{2}O$ and HCCH, using the accurate structural data available from microwave spectroscopic studies on several B:HX complexes, where B is a hydrogen bond $acceptor^{a}$. For $H_{2}S$, the available data is limited compared to other hydrogen bond donors listed above. Hence, a systematic investigation has been started on several $H_{2}S$ complexes. Several transitions have been observed for $Ar-(H_{2}S)_{2}$ and $C_{2}H_{4}-H_{2}S$ complexes. The rotational spectrum of $C_{2}H_{4}-H_{2}S$ complex appears to be a composite of rotational spectra of the hydrogen bonded $C_{2}H_{4}-H_{2}O$ and the van der Waals complex $C_{2}H_{4}-Ar$. Each transition is split in to four with a smaller splitting of about 0.14 MHz and a larger splitting of 1.67 MHz in $(B+C)/2$. The rotational constants for the strongest progression are $A = 26(1)$ GHz; $B = 1972.88(1)$ MHz and $c = 1866.68(1)$ MHz. Assignment of $Ar-(H_{2}S)_{2}$ spectra is in progress. It was realized that the rotational spectrum for $(H_{2}S)_{2}$ complex has not been completely solved $yet^{b}$ and hence a 'revisit' started. Several more progressions have been assigned for this dimer now. The search for deuterated isotopomers was carried out by bubbling $H_{2}S$ through $D_{2}O$ and some new $H_{2}O-H_{2}S$ transitions have been observed. During this talk, rotational spectra of all these complexes will be discussed.

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$^{a}$P. K. Mandal and E. Arunan J. Chem. Phys. 114, 3880 (2001) $^{b}$F. J. Lovas private communication
Author Institution: Department of Inorganic and Physical Chemistry, Indian Institute of Science

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