INFRARED SPECTRA OF $ZrH_{4}$ AND $HfH_{4}$ IN SOLID ARGON

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1995

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Ohio State University

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Abstract

Reactions of pulsed laser evaporated Zr and Hf atoms with $H_{2}$ during condensation in excess argon give strong infrared absorptions at 1623.6 and $1678.4 cm^{-1}$. These bands are assigned, respectively, to the antisymmetric stretching fundamentals of the tetrahedral $ZrH_{4}$ and $HfH_{4}$ molecules experimentally observed here for the first time. Perdeutero counterparts were observed at 1166.6 and $1201.7 cm^{-1}$, respectively. Confirmation of the tetrahydride identification is found in the four bands observed for the HD reaction products, which are due to symmetric and antisymmetric $M-H_{2}$ and $-D_{2}$ stretching modes for the $MH_{2}D_{2}$ molecules. Lanthanide contraction and relativistic effects cause the fundamental for $HfH_{4}$ to be slightly higher than that for $ZrH_{4}$.

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Author Institution: University of Virginia, Charlottesville, VA 22901

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