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At least 19 records

Xenon fluorides show potential as fluorinating agents

Xenon fluorides permit the controlled addition of fluorine across an olefinic double bond. They provide a series of fluorinating agents that permit ready separation from the product at a high purity. The reactions may be carried out in the vapor phase.

Chernick, C. L.↗

Xenon fluoride solutions effective as fluorinating agents

Solutions of xenon fluorides in anhydrous hydrogen fluoride have few disruptive effects and leave a residue consisting of gaseous xenon, which can be recovered and refluorinated. This mild agent can be used with materials which normally must be fluorinated with fluorine alone at high temperatures.

Hyman, H. H.↗

Inner-shell photoionization and core-hole decay of Xe and XeF{sub 2}

Photoionization cross sections and partial ion yields of Xe and XeF{sub 2} from Xe 3d{sub 5/2}, Xe 3d{sub 3/2}, and F 1s subshells in the 660–740 eV range are compared to explore effects of the F ligands. The Xe 3d-ϵf continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF{sub 2} cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. Comparisons of the ion products from the atom and molecule following Xe 3d photoionization show that the charge-state distribution of Xe ions is shifted to lower charge states in the molecule along with production of energetic F{sup +} and F{sup 2+} ions. This suggests that, in decay of a Xe 3d core hole, charge is redistributed to the F ligands and the system dissociates due to Coulomb repulsion. The ion products from excitation of the F 1s-LUMO resonance are different and show strong increases in the yields of Xe{sup +} and F{sup +} ions. The subshell ionization thresholds, the LUMO resonance energies, and their oscillator strengths are calculated by relativistic coupled-cluster methods and agree well with measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excimer lasers

The results of a two-year investigation into the possibility of developing continuous wave excimer lasers are reported. The program included the evaluation and selection of candidate molecular systems and discharge pumping techniques. The K Ar/K2 excimer dimer molecules and the xenon fluoride excimer molecule were selected for study; each used a transverse and capillary discharges pumping technique. Experimental and theoretical studies of each of the two discharge techniques applied to each of the two molecular systems are reported. Discharge stability and fluorine consumption were found to be the principle impediments to extending the XeF excimer laser into the continuous wave regime. Potassium vapor handling problems were the principal difficulty in achieving laser action on the K Ar/K2 system. Of the four molecular systems and pumping techniques explored, the capillary discharge pumped K Ar/K2 system appears to be the most likely candidate for demonstrating continuous wave excimer laser action primarily because of its predicted lower pumping threshold and a demonstrated discharge stability advantage.

Palmer, A. J.↗

Ultraviolet lasers. Citations from the International Aerospace Abstracts data base

Reports cited from the international literature describe various aspects of ultraviolet lasers including laser output, far ultraviolet radiation, electron pumping, optical pumping, and laser materials. Gas lasers, pulsed lasers, dye lasers, CO2 lasers, xenon fluoride lasers, and transversely excited atmospheric (TEA) lasers are considered. This updated bibliography contains 283 citations, 66 of which are new additions to the previous edition.

Mauk, S. C.↗

Pure xenon hexafluoride prepared for thermal properties studies

Preparation of a xenon hexafluoride and sodium fluoride salt yields a sample of the highest possible purity for use in thermal measurements. The desired hexafluoride can easily be freed from the common contaminants, xenon tetra-fluoride, xenon difluoride, and xenon oxide tetrafluoride, because none of these compounds reacts with sodium fluoride.

Malm, J. G.↗

Fluorinated noble-gas cyanides FKrCN, FXeCN, and FXeNC

We report on three new noble-gas molecules, FKrCN, FXeCN, and FXeNC, prepared in low-temperature Kr and Xe matrices. These molecules are made by UV photolysis of FCN in the matrices and subsequent thermal annealing. The FCN precursor is produced by deposition of the matrix gas containing (FCN){sub 3} through a microwave discharge. The new noble-gas molecules are assigned with the help of quantum chemical calculations at the MP2(full) and CCSD(T) levels of theory. Similar Ar compounds (FArCN and FArNC) as well as FKrNC are not found in these experiments, which is in agreement with the calculated energetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pulsed Gas Lasers Pumped by a Runaway Electron Initiated Discharge

The generation parameters are investigated in a runaway electron preionized diffuse discharge (REP DD). Laser generation is produced in different spectral bands from the IR to VUV range. New modes of the nitrogen laser operation are obtained. Ultimate efficiencies of N{sub 2}- and nonchain HF(DF)-lasers are achieved. A possibility of increasing the pulse durations of XeF-, KrF-, ArF- and VUV F{sub 2}- lasers (157 nm) in an oscillating REP DD is shown. The efficiencies of VUV- and UV-generation comparable with that of a laser pumped by a self-sustained volume discharge with preionization are gained.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

THL-100 Multi-Terawatt Laser System of Visible Range

Results of investigation of the parameters of the THL-100 hybrid laser system of visible range developed at the IHCE SB RAS in collaboration with the LPI RAS are presented. The laser system consists of the Ti:Sa Start-480M starting complex and the photodissociation XeF(C-A) amplifier with aperture of 24 cm. The starting complex provides 50-fs spectrally limited radiation pulses with energy of the second harmonic (475 nm) up to 20 mJ and 50-ps positively chirped radiation pulses with energy up to 5 mJ. The active medium of the XeF(CA) amplifier is created in the XeF{sub 2}/N{sub 2} mixture upon exposure to VUV radiation of xenon excited by a highpower electron beam. It is demonstrated that record power of 14 TW is attained by amplification of negatively chirped radiation pulse with duration of 1.6 ps in the XeF(C-A) amplifier, and maximum energy of ~3.2 J is realized by amplification of positively chirped radiation pulse.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural and magnetic behavior of the cubic oxyfluoride SrFeO{sub 2}F studied by neutron diffraction

The oxyfluoride SrFeO{sub 2}F has been prepared via a low temperature route involving the infinite-layer SrFeO{sub 2} and XeF{sub 2}. SrFeO{sub 2}F crystallizes in the cubic space group Pm-3m with disordered oxygen and fluorine atoms on the anion site. Recent reports demonstrated that SrFeO{sub 2}F is antiferromagnetic at room temperature and the zero field cooled and field cooled curves diverge at ∼150 K and ∼60 K, suggesting that the material has a spin glassy magnetic state at low temperatures. In this article, variable-temperature neutron diffraction (4–723 K) was performed to clarify the magnetic behavior observed in this material. Neutron powder diffraction measurements confirmed the antiferromagnetic (AFM) ordering of the system at room temperature. Below 710(1) K, the magnetic structure is a G-type AFM structure characterized by a propagation vector k=(1/2 , 1/2 , 1/2 ). The ordered moments on Fe{sup 3+} are 4.35(6)µ{sub B} at 4 K and 4.04(5)µ{sub B} at 290 K. Our results indicate that the cubic structure is retained all the way to base temperature (4 K) in contrast to PbFeO{sub 2}F. These results are compared with those of Pb and Ba analogs which exhibit very similar magnetic behavior. Furthermore, the observation of magnetic reflections at 4 K in the diffraction pattern shows the absence of the previously proposed spin glassy behavior at low temperatures. Previous proposals to explain the ZFC/FC divergences are examined. - Graphical abstract: Variable temperature powder neutron diffraction was employed to follow the evolution of the long range antiferromagnetic state in SrFeO{sub 2}F. - Highlights: • SrFeO{sub 2}F prepared via low temperature route involving SrFeO{sub 2} and XeF{sub 2}. • The cubic structure, Pm-3m, is retained at low temperatures, 4 K. • The magnetic structure is G-type AFM with T{sub N}=710 K and Fe{sup 3+} moment of 4.35µ{sub B}. • A small volume, bulk decoupled, spin glassy domain/cluster mechanism is proposed. • Highest AFM ordering temperature compared to Pb and Ba analogs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mushroom plasmonic metamaterial infrared absorbers

There has been a considerable amount of interest in the development of various types of electromagnetic wave absorbers for use in different wavelength ranges. In particular, infrared (IR) absorbers with wavelength selectivity can be applied to advanced uncooled IR sensors, which would be capable of identifying objects through their radiation spectrum. In the present study, mushroom plasmonic metamaterial absorbers (MPMAs) for the IR wavelength region were designed and fabricated. The MPMAs consist of a periodic array of thin metal micropatches connected to a thin metal plate with narrow silicon (Si) posts. A Si post height of 200 nm was achieved by isotropic XeF{sub 2} etching of a thin Si layer sandwiched between metal plates. This fabrication procedure is relatively simple and is consistent with complementary metal oxide semiconductor technology. The absorption spectra of the fabricated MPMAs were experimentally measured. In addition, theoretical calculations of their absorption properties were conducted using rigorous coupled wave analysis. Both the calculated and measured absorbance results demonstrated that these MPMAs can realize strong selective absorption at wavelengths beyond the period of the array by varying the micropatch width. Absorbance values greater than 90% were achieved. Dual- or single-mode absorption can also be selected by varying the width of the Si posts. Pixel structures using such MPMAs could be used as high responsivity, high resolution and fast uncooled IR sensors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Relativistic coupled-cluster calculations on XeF{sub 6}: Delicate interplay between electron-correlation and basis-set effects

A systematic relativistic coupled-cluster study is reported on the harmonic vibrational frequencies of the O{sub h}, C{sub 3v}, and C{sub 2v} conformers of XeF{sub 6}, with scalar-relativistic effects efficiently treated using the spin-free exact two-component theory in its one-electron variant (SFX2C-1e). Atomic natural orbital type basis sets recontracted for the SFX2C-1e scheme have been shown to provide rapid basis-set convergence for the vibrational frequencies. SFX2C-1e as well as complementary pseudopotential based computations consistently predicts that both O{sub h} and C{sub 3v} structures are local minima on the potential energy surface, while the C{sub 2v} structure is a transition state. Qualitative disagreement between the present results for the O{sub h} structure and those from CCSD(T)-F12b calculations [Peterson et al., J. Phys. Chem. A 116, 9777 (2012)], which yielded a triply degenerate imaginary frequency for the O{sub h} structure, is attributed here to the high sensitivity of the computed harmonic frequencies of the t{sub 1u} bending modes to the basis-set effects of triples contributions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phonocatalysis. An ab initio simulation experiment

Using simulations, we postulate and show that heterocatalysis on large-bandgap semiconductors can be controlled by substrate phonons, i.e., phonocatalysis. With ab initio calculations, including molecular dynamic simulations, the chemisorbed dissociation of XeF{sub 6} on h-BN surface leads to formation of XeF{sub 4} and two surface F/h-BN bonds. The reaction pathway and energies are evaluated, and the sorption and reaction emitted/absorbed phonons are identified through spectral analysis of the surface atomic motion. Due to large bandgap, the atomic vibration (phonon) energy transfer channels dominate and among them is the match between the F/h-BN covalent bond stretching and the optical phonons. We show that the chemisorbed dissociation (the pathway activation ascent) requires absorption of large-energy optical phonons. Then using progressively heavier isotopes of B and N atoms, we show that limiting these high-energy optical phonons inhibits the chemisorbed dissociation, i.e., controllable phonocatalysis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Design criteria for XeF{sub 2} enabled deterministic transformation of bulk silicon (100) into flexible silicon layer

Isotropic etching of bulk silicon (100) using Xenon Difluoride (XeF{sub 2}) gas presents a unique opportunity to undercut and release ultra-thin flexible silicon layers with pre-fabricated state-of-the-art Complementary Metal Oxide Semiconductor (CMOS) electronics. In this work, we present design criteria and mechanism with a comprehensive mathematical model for this method. We consider various trench geometries and parametrize important metrics such as etch time, number of cycles and area efficiency in terms of the trench diameter and spacing so that optimization can be done for specific applications. From our theoretical analysis, we conclude that a honeycomb-inspired hexagonal distribution of trenches can produce the most efficient release of ultra-thin flexible silicon layers in terms of the number of etch cycles, while a rectangular distribution of circular trenches provides the most area efficient design. The theoretical results are verified by fabricating and releasing (varying sizes) flexible silicon layers. We observe uniform translation of design criteria into practice for etch distances and number of etch cycles, using reaction efficiency as a fitting parameter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cooling molten salt reactors using “gas-lift”

This study briefly describes the selection of a type of two-phase flow, suitable for intensifying the natural flow of nuclear reactors with liquid fuel - cooling mixture molten salts and the description of a “Two-phase flow demonstrator” (TFD) used for experimental study of the “gas-lift” system and its influence on the support of natural convection. The measuring device and the application of the TDF device is described. The work serves as a model system for “gas-lift” (replacing the classic pump in the primary circuit) for high temperature MSR planned for hydrogen production. An experimental facility was proposed on the basis of which is currently being built an experimental loop containing the generator, separator bubbles and necessary accessories. This loop will model the removal of gaseous fission products and tritium. The cleaning of the fuel mixture of fluoride salts eliminates problems from Xenon poisoning in classical reactors.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

A large area imaging gas scintillation proportional counter for use in X-ray astronomy

A large area (200 sq cm), broad bandwidth (0.1-70 keV), imaging gas scintillation proportional counter (IGSPC) has been constructed for use in X-ray astronomy. The IGSPC consists of a high pressure xenon gas scintillation proportional counter (GSPC) coupled to a multi-wire proportional counter (MWPC) via a calcium fluoride window. THe MWPC, filled with a mixture of argon, methane, and tetrakis (dimethylamino) ethylene, detects the UV photons emitted by the xenon gas in the GSPC. The detector has a measured energy resolution of 8.0 percent (FWHM) and 4.3 percent (FWHM) at 5.9 keV and 22.1 keV, respectively. The predicted spatial resolution of the detector is less than 1 mm (FWHM) between 3-22 keV and 37-60 keV. A method to determine the three-dimensional location of detected X-rays is described. In addition, a combination of discrimination schemes designed to reduce the non-X-ray background in the IGSPC by more than two orders of magnitude is discussed.

Ku, W. H.-M.↗

Initial experimental demonstration of the principles of a xenon gas shield designed to protect optical components from soft x-ray induced opacity (blanking) in high energy density experiments

The design principles of a xenon gas shield device that is intended to protect optical components from x-ray induced opacity (“x-ray blanking”) have been experimentally demonstrated at the OMEGA-60 Laser Facility at the Laboratory for Laser Energetics, University of Rochester. A volume of xenon gas placed in front of an optical component absorbs the incoming soft x-ray radiation but transmits optical and ultra-violet radiation. The time-resolved optical (532 nm) transmission of samples was recorded as they were exposed to soft x-rays produced by a gold sphere source (1.5 kJ sr $-$1 , 250–300 eV). Blanking of fused silica (SiO 2 ) was measured to occur over a range of time-integrated soft x-ray (<3 keV) fluence from ~0.2–2.5 J cm $-$2 . A shield test device consisting of a 30 nm silicon nitride (Si 3 N 4 ) and a 10 cm long volume of 0.04 bar xenon gas succeeded in delaying loss of transmission through a magnesium fluoride sample; optical transmission was observed over a longer period than for the unprotected sample. It is hoped that the design of this x-ray shield can be scaled in order to produce a shield device for the National Ignition Facility optical Thomson scattering collection telescope, in order to allow measurements of hohlraum plasma conditions produced in inertial confinement fusion experiments. Finally, if successful, it will also have applications in many other high energy density experiments where optical and ultra-violet measurements are desirable.

42 ENGINEERING↗

High-power gas-discharge excimer ArF, KrCl, KrF and XeCl lasers utilising two-component gas mixtures without a buffer gas

Results of an experimental study of the influence of a gas mixture (laser active medium) composition on an output energy and total efficiency of gas-discharge excimer lasers on ArF* (193 nm), KrCl* (222 nm), KrF* (248 nm) and XeCl* (308 nm) molecules operating without a buffer gas are presented. The optimal ratios of gas components (from the viewpoint of a maximum output energy) of an active medium are found, which provide an efficient operation of laser sources. It is experimentally confirmed that for gas-discharge excimer lasers on halogenides of inert gases the presence of a buffer gas in an active medium is not a necessary condition for efficient operation. For the first time, in two-component gas mixtures of repetitively pulsed gas-discharge excimer lasers on electron transitions of excimer molecules ArF*, KrCl*, KrF* and XeCl*, the pulsed energy of laser radiation obtained under pumping by a transverse volume electric discharge in a low-pressure gas mixture without a buffer gas reached up to 170 mJ and a high pulsed output power (of up to 24 MW) was obtained at a FWHM duration of the KrF-laser pulse of 7 ns. The maximal total efficiency obtained in the experiment with two-component gas mixtures of KrF and XeCl lasers was 0.8%. (lasers)

74 ATOMIC AND MOLECULAR PHYSICS↗