Abstract

Infrared and Raman spectra are reported for Xe16O4 and Xe18O4 vapor. The infrared band contours are analyzed to give values for the Coriolis constants and the xenon isotopic frequency shift, and anharmonicity corrections are estimated for the fundamental frequencies. General quadratic force constants are calculated, using as constraints the O16–18O and Xe129–132Xe frequency shifts and the Coriolis constants. The force field is significantly different from those of RuO4 and OsO4. Valence stretching force constants are fr=6.40 ± 0.10 mdyn/Å and frr=−0.08 ± 0.04 mdyn/Å; the negative value of the interaction constant frr indicates that the bonding differs appreciably from that in the transition metal tetroxides. Standard-state thermodynamic functions for XeO4 vapor are calculated for the temperature range 250–400°K.

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