THE STRUCTURE OF $Kr-PF_{3}$ DETERMINED FROM THE NUCLEAR QUADRUPOLE COUPLING CONSTANTS OF $^{83}Kr-PF_{3}$

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1989

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Ohio State University

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The $^{83}Kr$ nuclear quadrupole coupling constants were measured for the $Kr-PF_{3}$ complex using a FTMW spectrometer. These values were compared with those expected from the Sternheimer equation $q_{i} = q_{i} (1--- \gamma_{\infty})$ for four possible structures which are consistent with the rotational constants. The value of $q_{i}^{\circ}$ (field gradient arising from $PF_{3}$) for each structure was calculated using GAUSSIAN86 for free $PF_{3}$. Information on $\gamma_{\infty}$ (Sternheimer shielding factor) necessary for the analysis was obtained by comparison with other $^{83}{Kr}$ complexes in the literature. The conclusion was that only one structure is consistent with the quadrupole coupling constants viz the conformation placing the Kr over a $PF_{2}$ face. A comparison between ab initio calculations and a multipole expansion approximation to estimate the electric field gradient at the rare gas site in van der Waals complexes will be presented.

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Author Institution: Department of Chemistry, University of Michigan

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