Raman Spectra and Force Constants for OsO4 and XeO4

Abstract

Raman spectra are presented for OsO4 vapor, and for XeO4 vapor and solid. Observed fundamental frequencies (in cm−1) for gaseous OsO4 are 965.2(a1), 333.1(e), 960.1(f2), and 322.7(f2). For XeO4 they are 773(a1) for the vapor, and 767.1(a1), 277(e), 867(f2), and 303-f2) for the solid. The Urey–Bradley constant F is 0.32 for OsO4, and −0.18 mdyn/Å for XeO4.

Ultraviolet Photolysis Studies on XeO4 in Noble‐Gas and F2 Matrices and the Formation and Characterization of a New XeVIII Oxide, (η2‐O2)XeO3

“…The far‐IR spectrum was measured in a neon matrix and showed a band at 305.7 cm −1 and a weaker broad band at 296.5 cm −1 , which are assigned to the split asymmetric XeO 4 bending mode ν 4 (T 2 ). The frequencies of both sets of split bands are in good agreement with those obtained from the Raman spectra of gaseous8 and solid7 XeO 4 and for XeO 4 dissolved in HF 8. In neon and argon matrices, the natural‐abundance isotopic pattern of the ν 3 (T 2 ) band was sufficiently well resolved to allow assignment of isotopically shifted bands associated with the most abundant xenon isotopes (Figure 1 and Table 1).…”

“…The energy change caused by this distortion would be about 7.3 kJ mol −1 , which is unlikely under these conditions. The third possibility, that is, the presence of inhomogeneous areas in the matrix that contain solid XeO 4 , seems plausible and is supported by the work of Huston and Claasen,7 who measured the Raman spectrum of XeO 4 at −196 °C and assigned bands to solid XeO 4 at 867 and 303 cm −1 . The band observed at 866.0 cm −1 in the present work is in excellent agreement with the reported value.…”

“…Despite their hazardous natures, the molecular structures of XeO 3 and XeO 4 have been obtained from a single‐crystal X‐ray diffraction study on XeO 3 4 and an electron diffraction study on gaseous XeO 4 5. Vibrational frequencies for XeO 4 have been previously obtained by gas‐phase IR spectroscopy6 and by Raman spectroscopy in the solid state7 and in anhydrous HF 8…”

Xenon and Argon: A contrasting behavior in olivine at depth

“…Other effects are expected to increase this fractionation. The difference in bond stiffness is expected to be greater between fluid Xe/Xe in silicate than between metal Si/Si in silicates as fluid Xe is not a metal unlike Si dissolved in Fe, and the Xe-O bond stiffness in the XeO 4 molecule is even higher than that of Si-O bond in olivine: 628 N m À1 (Huston and Claassen, 1970) vs. 347 N m À1 (Oehler and Gunnthard, 1969). P is not expected to have a strong effect (Shahar et al, 2009) apart from inducing the Xe/Si substitution.…”

Raman and IR spectra of matrix isolated OsO3F2 AND OsO4: The molecular shape of monomeric OsO3F2

“…Subsequent Raman studies of the vapour by Huston and Claassen [14] yielded v Z ( E ) at 333.1 cm-' and vq(T2) at 322.7 cm-', but according to McDowell and Goldblatt [15] the IR spectrum of the vapour shows the Q branch of v, at 329.0cm-'. Subsequent Raman studies of the vapour by Huston and Claassen [14] yielded v Z ( E ) at 333.1 cm-' and vq(T2) at 322.7 cm-', but according to McDowell and Goldblatt [15] the IR spectrum of the vapour shows the Q branch of v, at 329.0cm-'.…”