On existence and properties of plutonium(VIII) derivatives

Abstract

The existence of Pu(VIII) was shown in alkaline solutions and in nonpolar solvents (CCl₄ and CHCl₃) on the ground of such experimental facts like extraction of plutonium species, obtained by means of ozonization of Pu(VI) alkaline solutions into CCl₄ and CHCl₃; volatility of Pu compounds out of aqueous alkaline solutions, and the mentioned solvents. The product of interaction between PuO₃ · 0.8H₂O and XeF₂ in CCl₄ and CHCl₃ was of the same chemical form for both cases and identical with the form of the product of volatility of Pu out of these organic solutions. The electronic absorbance spectra of these products in CCl₄ and CHCl₃ were fairly similar to the ones for OsO₄ and RuO₄. The band of absorption in these spectra with the maximum at 332 nm corresponds to the charge transfer of metal-ligand type [π(O)→Pu], as the value of molar extinction coefficient ε was found to be higher than 2 · 10³ L/mole cm. A satisfactory agreement between the energies for the transitions of PuO₄ molecule designed by X_α-SW method and experimental data was observed. A similar accordance was observed for the designed vibration frequency (DFT-method) with the one found as result of analysis of the vibration structure of the experimental spectra.