STRUCTURE AND SPECTRA OF $UO_{2}F_{2}$

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2000

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Ohio State University

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Uranyl fluoride ($UO_{2}F_{2}$) is a product of the reaction $UF_{6}$ with moisture. There are ca. 200,000 tons of (depleted) $UF_{6}$ stored in Ohio and ca. 500,000 tons stored in Kentucky. Thus the detection of a luminescent product of leaking $UF_{6}$ with (humid) air may be useful. Studies of solutions containing $UO_{2}F^{2-n}_{n}$ species have shown that $UO_{2}F_{2}$. Initially we were studying the isolated molecule, but we added solvating water molecule (probably 3), and optimized the structure to get the spectra for species in solution. Solvation effects for this neural molecule are presumably smaller than those for ions. We use relastivistic core potentials to replace the core electrons on all atoms, leaving 50 valence electrons to be treated (courtesy of D.A. Dixon) to give a (non-planar) $C_{2v}$ structure. MOs are obtained from SCF and MCSCF calculations. The spin-orbit interaction and electron correlation are included using spin-orbit configuration interaction (SO-GUGA in the Columbus programs). Spin-orbit and equatorial-ligand ($F^{-}, H_{2}O$) interactions compete in determining the splittings of the known ($^{3}\Delta_{g}$) luminescent state of the uranyl ion.

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Author Institution: Department of Chemistry, The Ohio State University

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