On existence and properties of plutonium(VIII) derivatives

被引:5
作者
Kiselev, Yu M. [2 ]
Nikonov, M. V. [1 ]
Dolzhenko, V. D. [2 ]
Ermilov, A. Yu [2 ]
Tananaev, I. G. [3 ]
Myasoedov, B. F. [1 ]
机构
[1] Russian Acad Sci, Inst Geochem & Analyt Chem, Moscow 119334, Russia
[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia
[3] Russian Acad Sci, Inst Phys Chem & Electrochemiostry, Moscow 119071, Russia
基金
俄罗斯基础研究基金会;
关键词
Plutonium; Tetraoxide of plutonium; Electron absorption spectra of tetraoxide of plutonium; Volatility of tetraoxide of plutonium; Quantum chemical simulation of the structure of tetraoxide of plutonium; CRYSTAL-STRUCTURE; AB-INITIO; SPECTRA; VOLATILITY; STATES;
D O I
10.1515/ract-2014-2146
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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 center dot 0.8H(2)O 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 [pi(O)-> Pu], as the value of molar extinction coefficient.. was found to be higher than 2 x 10(3) L/mole cm. A satisfactory agreement between the energies for the transitions of PuO4 molecule designed by X-alpha-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.
引用
收藏
页码:227 / 237
页数:11
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