dc.creator Higgins, Kelly J. en_US dc.creator Tao, Fu-Ming en_US dc.creator Klemperer, William en_US dc.date.accessioned 2007-11-20T17:08:03Z dc.date.available 2007-11-20T17:08:03Z dc.date.issued 1995 en_US dc.identifier 1995-RD-03 en_US dc.identifier.uri http://hdl.handle.net/1811/29606 dc.description Author Institution: Harvard University, Cambridge. MA 02138. en_US dc.description.abstract We 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.extent 71807 bytes dc.format.mimetype image/jpeg dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title HeClF AND $(ClF)_{2}$: AB INITIO CALCULATIONS AND ROTATIONAL SPECTROSCOPY en_US dc.type article en_US
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