FOURIER TRANSFORM MICROWAVE SPECTROSCOPY OF THE HOSO RADICAL

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2011

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Ohio State University

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Molecules closely-related to SO$_2$ are of considerable interest because of the important role this triatomic or its surrogates play in the atmospheric and combustion chemistry of sulfur-containing compounds. Previous coupled-cluster quantum chemical calculations nderline{\textbf{95}}, 4940, (1991)} of the [HSO$_2$] potential energy surface conclude that a \emph{cis-}isomer is the ground state, the \emph{trans} isomer is a transition state, and that a $C_{2v}$ HSO$_2$ isomer lies considerably higher in energy ($\sim$~20~kcal/mol). Using Fourier Transform microwave spectroscopy, the rotational spectrum of the \emph{cis-}HOSO radical has been precisely characterized for the first time by applying a DC discharge to a mixture of water and sulfur dioxide heavily diluted in neon. The fundamental rotational transition was detected near 17 GHz, in good agreement (within $\sim$~1\%) of the calculated value derived from the equilibrium structure nderline{\textbf{421}}, 562, (2006)}. Microwave-microwave double resonance techniques have been used to extend the dataset to higher frequencies and to provide confirmation of the spectroscopic assignments.

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Author Institution: Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138, and School of Engineering and Applied Science, Harvard University, Cambridge, MA 02138; Dipartimento di Chimica Fisica e Inorganica, Universita di Bologna, V.le Risorgimento 4; I-40136 Bologna, Italy

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