The use of hexafluoropropene oxide in substitutive fluorination of SbV and BiV oxygen-containing compounds

Reactions of hexafluoropropene oxide with Sb^V and Bi^V oxygen-containing compounds were studied. The E=O (E−O) groups were found to be transformed into the EF₂ (E−F) (E=Sb or Bi) groups. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1652–1653, August, 1998.     

Detection of Gas Bubble by SIMS in Irradiated Nuclear Fuel

The formation of gas bubbles is a key issue for nuclear fuel behaviour. The first measurements of xenon during a depth profile in irradiated nuclear fuel evidenced some peaks over a non-zero baseline. In comparison with EPMA mappings of xenon and SEM image of the sputtered surface, it is proven that the peaks correspond to bubbles while the baseline corresponds to xenon included in the UO₂ matrix.     

Anomalous photo-ionization of 4d shell in medium-Z ionized atoms

Photoionization (PI) cross sections (PICS) are necessary for the simulation of astrophysical and ICF plasmas. In order to be used in plasma modeling, the PICS are usually fit to simple analytical formulas. We observed an unusual spectral shape of the PICS of the 4d shell of ionized Xe and other elements, computed with different codes: a local minimum occurs around twice the threshold energy. We explain this phenomenon as interference between the bound 4d wavefunction and the free electron wavefunction, which is similar to the Cooper minima for neutral atoms. Consequently, the usual fitting formulas, which consist of a combination of inverse powers of the frequency beyond threshold, may yield rates for PI and radiative recombination (RR) that are incorrect by orders of magnitude. A new fitting algorithm is proposed and is included in the latest version of HULLAC.v9.5.     

Photoelectron extraction efficiency from cesium iodide photocathodes in a pressurized atmosphere of argon and xenon up to 10 bar

Photoelectron extraction efficiency is a key parameter in gaseous detectors design requiring CsI photocathodes, particularly in pressurized applications for rare event experiments. Within this work we report on our measurements of the photoelectron extraction efficiency from a CsI photocathode into argon and xenon up to 10 atm. It is demonstrated that the photoelectron extraction efficiency is independent from pressure when scaling the electric field accordingly. This measurement provides experimental validation to the Monte Carlo predictions.     

The dependence on temperature and concentration of 129Xe NMR chemical shift values of organoxenon(II) salts [RXe][Y] and of the parent molecule XeF2

The dependence of the 129Xe NMR chemical shift value of XeF2 on temperature and concentration was determined in a variety of prototypic media: in acidic (anhydrous HF, aHF), nonprotic but polar (dichloromethane), and basic (CD3CN-EtCN, 1:3 v/v) solvents. The 129Xe NMR spectra of a representative series of organoxenon(II) salts [RXe][Y] (R = C6F5, heptafluoro-1,4-cyclohexadien-1-yl (cyclo-1,4-C6F7), pentafluoro-1,4-cyclohexadien-3-on-1-yl (cyclo-3-O-1,4-C6F5), CF2=C(CF3), (CF3)2CFC[triple bond]C, C4H9C[triple bond]C; Y = BF4, AsF6) in aHF showed, compared with XeF2-aHF, a quantitatively less distinct but qualitatively related dependence of delta(129Xe) vs temperature. The dependence of their delta(129Xe) values on concentration in aHF is negligible. An explanation for the different behavior of [RXe][Y] and XeF2 is offered.     

Crystal structure of boron difluoride acetylnaphtholates

The crystal structure of luminescent isomeric boron difluoride acetylnaphtholates: 2-acetyl-1-naphthoboron difluoride (1) and 1-acetyl-2-naphthoboron difluoride (2) has been studied. Molecules of 1 make infinite stacks of coplanar molecules in crystals, and molecules of 2 are arranged in the crystalline cell in the form of isolated π-dimers. Unlike a planar molecule of 1, the methyl group in α-position of the diketonate ring drops out of the molecule plane in a molecule of 2, thus forcing the chelate ring to bend considerably along the line C(11)-B. The structure features of 1 cause a bathochromic shift of the luminescence band in comparison with 2.     

光电子成像方法研究Xe时间分辨多光子电离过程

利用自行研制的离子成像检测器研究了Xe的飞秒时间分辨双色多光子电离过程.Xe的408nm多光子电离对比实验结果表明,该离子成像检测器与相应的进口产品具有相近的光电子能量分辨率.在272nm飞秒激光作用下,3光子电离产生能量为1.57和0.26eV的光电子,分别对应于Xe+的两个自旋态;在408nm飞秒激光作用下,还观察到第一级阈上电离产生的光电子.在双色飞秒时间分辨实验中,随着两束光相对时间的改变,光电子能谱出现了一系列的变化;随着两束光时间重合程度的增加,由双色多光子电离(3+1'或4'+1)产生的光电子信号逐渐加强;在第二束光的作用下,由第一束单色光产生的光电子出现能量红移,第二束光同时也导致中间态布居数减少.这种光电子能谱的红移现象反映了原子体系中激光场诱导有质动力势的时间分辨动态调制过程.     

Electrochemical fluorosulfation of perfluoroalkyl vinyl ethers

The reaction of perfluoroalkyl vinyl ethers with electrochemically generated peroxydisulfuryl difluoride produces a mixture of α,ω-bis-fluorosulfonyloxy(perfluoroalkoxyalkanes). The fluorosulfate dimers of the starting vinyl ethers prevailing in the reaction mixture were transformed into perfluoro-2,3-dialkoxysuccinyl difluorides. High stability of intermediate radicals, in which the radical center is adjacent to the oxygen atom, is one of the factors determining the compositions of the reaction products. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1884–1889, August, 2005.     

An ab initio and DFT study on the hydrolysis of carbonyl dichloride

Hydrolysis of carbonyl dichloride or phosgene (Cl₂CO) in gas phase has been investigated at Hartree–Fock, density functional and ab initio levels of theory. The effects of basis sets on the energetics of the reaction have also been explored. Calculations reveal that initially carbonyl dichloride and water form a weak complex and this complex can react further in two ways. In Path 1, water adds on to carbonyl dichloride across carbonyl bond in a concerted fashion to give dichloromethane diol, and this diol decomposes to form chloro formic acid by syn-1,2-elimination of HCl and forms CO₂ and HCl as final products. Path 2 is the concerted addition of water across carbon chlorine bond and elimination of HCl in a single step leading to the formation of chloro formic acid directly. This second path that skips the formation of dichloromethane diol is observed to be very low lying and hence is kinetically favored. Addition of second water molecule to the reacting system is found to catalyze the reaction by stabilizing the complex, intermediate and transition states and reduces the activation energy to 24.6 kcal mol⁻¹ compared to 29.9 kcal mol⁻¹ for a single water molecule.