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dc.creatorHiggins, Kelly J.en_US
dc.creatorTao, Fu-Mingen_US
dc.creatorKlemperer, Williamen_US
dc.date.accessioned2007-11-20T17:08:03Z
dc.date.available2007-11-20T17:08:03Z
dc.date.issued1995en_US
dc.identifier1995-RD-03en_US
dc.identifier.urihttp://hdl.handle.net/1811/29606
dc.descriptionAuthor Institution: Harvard University, Cambridge. MA 02138.en_US
dc.description.abstractWe report ab initio and experimental studies of HeClF and $(ClF)_{2}$. Microwave electric resonance optothermal spectroscopy guided by ab initio potential energy surface and the resultant calculated vibrational and rotational states were used to observe rotational transitions of the two complexes. The HeClF potential energy surface was calculated at the MP4 level using a large basis set containing bond functions. The surface is characterized by three distinct minima with the global minimum at the linear He-Cl-F and two others at a nearly T-shaped and at the anti-linear He-F-Cl configurations. The bound state calculations were performed using the collocation method with a large basis set. Predicted bound states fall into three catagories with the He atom localized either in the linear He-Cl-F, a mixture of the T-shaped and anti-linear He-F-Cl, or the anti-linear He-F-Cl configurations. These calculations were then used to guide the experimental search for transitions. The $J = 1 \leftarrow 0 and J = 2 \leftarrow 1$ transitions for overall rotation of the linear structure were observed within 2% of theoretical values. The resolved hyperfine structure allowed determination of the quadrupole coupling constants for the two excited rotational states. For $He^{35}ClF$ the spectroscopic constants are $B = 5586.417(20) MHz, D = 1.370(5) MHz, eqQ_{J=2} = -133.70(6) MHz, and eqQ_{J=1} = - 133.79(6) MHz$. Rotational transitions of the three most abundant $(ClF)_{2}$ isotopomers were also observed experimentally. These are attributed to $(ClF)_{2}$ on the basis of MP2 level geometry optimizations. The calculated equilibrium structure is L shaped with nearly linear $F-Cl\cdots F, a Cl\cdots F$ van der Waals bond distance $2.8 {\AA}$ and the $Cl\cdots F-Cl$ angle $112^{\circ}$. For $(^{35}ClF)_{2} J = 6 \leftarrow 5$ and $J = 7 \leftarrow 6$ transitions were observed at 13.0 GHz and 15.1 GHz respectively.en_US
dc.format.extent71807 bytes
dc.format.mimetypeimage/jpeg
dc.language.isoEnglishen_US
dc.publisherOhio State Universityen_US
dc.titleHeClF AND $(ClF)_{2}$: AB INITIO CALCULATIONS AND ROTATIONAL SPECTROSCOPYen_US
dc.typearticleen_US


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