Infrared spectra and geometry of matrix isolated rare-earth and IIIB metal fluorides Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/t435gh88r

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  • The infrared absorption spectra (40-800 cm⁻¹) of the trifluorides of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm, and Yb isolated in solid argon, krypton and nitrogen matrices have been obtained. For PrF₃ the symmetric and asymmetric stretching modes were observed; PrF₃ is accordingly assigned a pyramidal configuration. All of the other molecules, except NdF₃, exhibited only the asymmetric stretching mode and hence are assigned a planar configuration. At present, the spectrum of NdF₃ cannot be satisfactorily interpreted, but a number of possibilities are explored. The low frequency modes, v₂ and v₄, were also observed for Sc-, Y-, La-, Ce-, Pr-, Nd-, Sm-, Eu-, Ho-, and YbF₃, Using a valence force field approximation, force constants have been derived from the measured fundamental frequencies and the infrared inactive symmetric stretching frequency of many of the planar molecules has been estimated. For several of these compounds statistical entropies have also been calculated from the vibrational data and molecular geometries and are compared with Third Law values.
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