Improved separation of the rare sulfur isotopes by infrared multiphoton dissociation of SF6

The dissociation probabilities of³²SF₆ and some of³⁴SF₆ have been measured at a large number of CO₂ laser lines both at room temperature and at 140 K. The longwavelength wing of this dissociation spectrum is exponential in the wavenumber. Its logarithmic slope is proportional to the inverse temperature. Selectivities are high enough at 140 K, that the photons are consumed only for the rare isotope in the case of³⁴SF₆ and nearly so for³⁶SF₆. For³³SF₆ further improvement of the selectivity would be desirable.     

Pressure-broadened linewidths of hydrogen sulfide

Self-broadened and foreign-gas (N₂ and O₂) broadened linewidths of H₂S at 300°K have been calculated using the Anderson-Tsao-Curnutte theory of line broadening for a wide range of quantum numbers J and K_a, in both type A and type B bands. Computed values for self-broadened linewidths are in good agreement with the experimental results of Helminger and De Lucia. Air-broadened linewidths of H₂S at 200°K have also been calculated, so that the temperature dependence can be estimated.     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

Pressure-broadened linewidths of ethylene

Self-Broadened and foreign-gas (N₂ and O₂) broadened linewidths of C₂H₄ at 300°K have been calculated using the Anderson-Tsao-Curnutte theory of line broadening for a wide range of quantum numbers J and K_α, for all three types of bands. The molecular quadrupole moment tensor of C₂H₄ is taken from Mulder and Huiszoon. Air-broadened linewidths of ethylene at 200°K have also been computed, so that the temperature dependence can be estimated.     

Mass spectrometry of arcs in SF6 circuit breakers

Today, SF₆ is used to a great extent as insulating and arc-quenching medium in high-voltage gas-blast circuit breakers. The arcing in SF₆ during current interruption forms decomposition products. These can influence the arc-quenching properties of the circuit breaker. Furthermore, they can cause corrosion of the circuit breaker housing. In this comprehensive study we present results obtained for the first time from a direct mass spectrometric investigation of the exhaust gases of a high pressure SF₆ arc in a model circuit breaker. Our mass spectrometric system consists of a time-of-flight mass spectrometer (TOFMS) equipped with a molecular beam sampling systems. This device allows us to measure mass spectra of high pressure sources with a time resolution of up to 10,000 spectra per second. We have determined the formation rate of the most abundant decomposition products in a SF₆ arc at 1 bar. These products are SF₄, CF₄, WF₆, SOF₂, SO₂, CS₂ S₂F₂ and HF. The fast detection time inherent to our system permits also the determination of the formation of SF₄, which is 0.45–0.50 Vol. %/(kJ/1SF₆). In addition, we have studied the influence of water and oxygen impurities which are responsible for the production of highly corrosive HF. Finally, we have considered the influence of the thermal degradation of teflon (P.T.F.E.), which is used as nozzle and insulating material in circuit breakers. On this occasion we have demonstrated that CF₄, which exhibits dielectric properties similar to SF₆, is the main decomposition product formed from teflon. However, we have found that besides CF₄ also excess carbon is formed, which is deposited on insulators of the model circuit breaker.Our time-resolved mass spectra reveal that the CF₄ production from teflon is delayed by a few milliseconds with respect to the SF₆ dissociation in the arc. This delay can influence the interrupting process of the circuit breaker by changing the plasma composition during the arcing period. Although our experiments have been performed on a model circuit breaker we claim that the results presented in this study can be applied to real circuit breakers, since the arc current density and the energy dissipated per liter SF₆ are of the same order of magnitude in both devices.     

ESR study on the structure of the ethylene radical cation stabilized in frozen SF6 and some fluoroalkanes: An evidence for a twisted structure

ESR spectra of the ethylene radical cation were detected at cryogenic temperatures in SF₆, C₂F₆ and C₃F₈. From the unusually small hyperfine couplings estimated for¹H and¹³C, it has been shown that the ethylene radical cation has a non-planar structure with a torsional angle in the range of 8°–23°. Upon annealing the sample at a temperature above 93 K, the ethylene radical cation in SF₆ changed into a monofluoroethyl radical through charge recombination with fluoride anion or SF ₆ ^? .     

The high temperature absorption of CO2 laser radiation by SF6, NF3, and NH3

The absorption coefficients of SF₆, NF₃ and NH₃ at CO₂ laser wavelengths have been evaluated at elevated temperatures in a shock tube study. Measurements were performed in the pressure range of P = 10−70 atm for temperatures between 500 and 2900 K. The effects of finite rate chemical decomposition on the absorption observations are discussed.     

Frequency measurements in the 10 μm spectrum of 11BCl3

This paper presents a study of the spectroscopy of ¹¹BCl₃ using the Doppler-free saturated absorption technique. Many lines in the degenerate ν₃ fundamental of this molecule have been recorded using the 10P branch of a carbon dioxide laser. The absolute frequencies of the linecentres of these absorptions have been measured to an accuracy of better than 10 kHz, using frequencies calibrated against transitions in SF₆ and OsO₄. Hyperfine structure due to the Cl nuclei was easily resolved, and more detailed structure, which may be attributed to the ¹¹B quadrupole interaction, was also seen. The splittings between individual quadrupole components were measured to an accuracy of better than 2 kHz where SF₆ references were used, and to about 8 kHz in the case of OsO₄. Peak-to-peak linewidths as low as 22 kHz have been recorded, representing the highest resolution data yet obtained for this molecule.     

IR multiphoton absorption of SF6 in flow with Ar at moderate energy fluences

6 in flow with Ar (SF₆: Ar=1:100) in conditions of a large vibrational/rotational temperature difference (T_V≃230 K, T_R≃60 K) was studied at moderate energy fluences from ≃0.1 to ≃100 mJ/cm², which are of interest for isotope selective two-step dissociation of molecules. A 50 cm Laval-type slit nozzle for the flow cooling, and a TEA CO₂-laser for excitation of molecules were used in the experiments. The laser energy fluence dependences of the SF₆ MPA were studied for several CO₂-laser lines which are in a good resonance with the linear absorption spectrum of the ν₃ vibration of SF₆ at low temperature. The effect of the laser pulse duration (intensity) on MPA of flow cooled SF₆ with Ar was also studied. The results are compared with those obtained in earlier studies. Received: 4 September 1995/Revised version: 15 February 1996     

Argon matrix Raman and infrared spectra of SF5Cl,SF5Br,and S2F10

Infrared and laser-excited Raman spectra of SF₅Cl, SF₅Br, and S₂F₁₀ have been observed in dilute argon matrices and in the solid phase at 8 K. The first vibrational assignment of the SF₅Br molecule and assignments for the ν(SCl), ν(SBr), and ν(SS) modes in SF₅Cl, SF₅Br, and S₂F₁₀ are presented. The chlorine isotopic components of the SCl stretch in SF₅Cl have been resolved. The Raman spectrum of SF₅Br, which has not been reported previously, is discussed.     

Measurements of thermal electron attachment rate coefficients to molecules using an electron swarm technique

An existing electron swarm apparatus has been redesigned and upgraded. In particular, the new design incorporates a novel planar radioactive foil to form an integral part of the drift tube, allowing us to overcome inherent problems present in our earlier system which used a cylindrical radioactive source. In addition to this, substantial upgrades have been made to improve the gating and amplification electronics and the data acquisition system. This has resulted in a much greater signal to noise ratio and improved accuracy. This paper describes the upgraded apparatus and its use in obtaining thermal (300 K) attachment rate coefficients to a number of molecules. The quality of the measurements and data are illustrated through the measurement of the thermal attachment rate coefficient for SF₆ (k_th(SF₆) = (2.38 ±0.15 ) ×10 ^-7 cm³ s^-1). Thermal electron attachment rate coefficients for four other molecules are presented, namely for two derivatives of SF₆, SF₅CF₃ and SF₅Cl, and two perfluorocarbons, c-C₄F₈ and 2-C₄F₈.     

The electric hyperfine interaction in group VI-a hexafluorides

The electric hyperfine interaction in group VI-a hexafluorides SF₆, SeF₆ and TeF₆ has been studied in the temperature range from 10 K to about 110K by means of the TDPAD method. The temperature dependence can be explained by Bayer — Kushida theory. The coupling constants decrease with increasing temperature. The strength of the temperature dependence diminishes from SF₆ to TeF₆, indicating an increase of ionicity of the bonds. If the coupling constants are plotted versus the elements of the fluorine compounds, characteristic trends can be seen. Therefore we predict the coupling constant of OF₂ to be about 100 MHzThis work was supported by the Bundesministerium für Forshung und Technologie     

Doppler-limited spectroscopy of the 3ν3 band of SF6

The strongest portion of the 3ν₃ band of SF₆ has been recorded at T = 160 and 295 K with Doppler-limited resolution using a tunable laser difference-frequency spectrometer. The structure in this band has been identified with the P, Q, and R branches of one F_1u sublevel (with essentially l = 1 character) within the 3ν₃ vibrational manifold. Preliminary effective rotational constants have been obtained for this band from which the anharmonic parameters X₃₃, G₃₃, and T₃₃ can be estimated. The role of hot bands and of the other anharmonic sublevels is discussed in relation to prior interpretations of low resolution spectra and of the initial isotope selective stages of CO₂ laser photo-dissociation of SF₆.     

High resolution study of anion formation in low-energy electron attachment to SF<Subscript>6</Subscript> molecules in a seeded supersonic beam

Using two variants of the Laser Photoelectron Attachment (LPA) method involving a differentially-pumped, seeded supersonic beam (0.05% and 12.5% of SF₆ molecules in helium carrier gas, nozzle temperatures T₀= 300–600 K, stagnation pressures p₀= 1–5 bar) and mass spectrometric ion detection, we have investigated the energy dependence of anion formation in low-energy electron collisions with SF₆ molecules at high energy resolution. Using the standard LPA method, the yield for SF₆^- as well as SF₅^- and F^- anions was studied with an energy width around 1 meV over the electron energy range 0–200 meV. In addition, a variant of the LPA method with extended energy range (denoted as EXLPA) was developed and applied to measure the yield for SF₆^- and SF₅^- formation over the energy range 0–1.5 eV with an energy width of about 20 meV. The cross-section for formation of SF₆^- decreases by five orders of magnitude over the range 1–500 meV and is only weakly dependent on nozzle temperature. The yield for SF₅^- formation shows — apart from a weak zero energy peak which grows strongly with rising temperature — a broad maximum (located around 0.6 eV for T₀= 300 K and shifting to lower energies with rising T₀) and a monotonical decrease towards higher energies. SF₅^- attachment spectra taken at elevated temperatures exhibit changes with rising stagnation pressure which directly reflect rovibrational cooling of the SF₆ molecules with rising pressure. The SF₅^-/SF₆^- intensity ratio at near-zero energy and the low-energy shape of the broad peak in the SF₅^- spectra are used as thermometers for the internal temperature of the SF₆ molecules in the seeded supersonic beam which (at p₀= 1 bar) are found to be 50–100 K lower than the nozzle temperature. The energy dependence of the yield for F^- formation is similar to that for SF₆^-, but the F^- signals are three to four orders of magnitude lower than those for SF₆^-; in view of the rather high endothermicity of F^- formation the origin of the F^- signals is discussed in some detail.     

Strong dependence of ir multiphoton absorption and dissociation yield of SF6 molecule on intensity (duration) of exciting laser pulse

The role of played by the intensity of the exciting TEA CO₂ laser pulses in the processes of ir multiphoton absorption (MPA) of SF₆ molecules cooled toT _R?40 K andT _v?160 K in a pulsed supersonic jet and the dissociation of SF₆ in a bulk atT?300 K under essentially collisionless conditions have been investigated. A strong dependence of MPA and the dissociation yield on pulse intensity were observed. The frequency dependences of the intensity effects were studied.     

X-ray photoemission study of physically absorbed SF6

The physical adsorption of octahedral SF₆ on Ru(001) has been studied with X-ray photoelectron spectroscopy (XPS) in an attempt to see effects on the energy levels resulting from the conformation of the molecule on the surface. Near 80 K surface coverages up to a monolayer have been studied at various steady state pressures of SF₆. Kinetic studies, core level binding energies, and peak areas indicate that the surface species studied was a physically adsorbed monolayer of sf₆. The sticking coefficient of SF₆, at ? 80 K is approximately unity. Also, a multilayer structure was observed at the highest pressures of SF₆. The binding energy of the F(ls) peak for monolayer coverage is centered at 688.2 ± 0.2 eV relative to the Ru Fermi level. while the multilayer F(ls) peak is shifted more than 3.5 eV to higher binding energy. The F(ls) linewidth for one monolayer has a full width at half maximum of 1.75 ± 0.1 eV. The F(ls) linewidth of the multilayer peak narrows with increasing coverage. Its narrowest observed linewidth was 1.35 eV ± 0.1 eV or approximately the same as that found in the gas phase. One of the mechanisms which may account for the F(ls) linewidth with monolayer coverage is a difference in F(ls) binding energy between those F atoms in contact with the substrate and those further away. This may be due to the variation in chemical environment and relaxation effects as a function of distance from tlie substrate. A classical image force calculation including finite screening effects of the substrate indicates that there is a differential binding energy, ΔW. between the F ligands; ΔW = 0.85 ± 0.25 eV, for realistic ranges of adsorption distances from the substrate and screening lengths in the substrate. The observed broadening of the monolayer F(ls) level is consistent with a ΔW of 0.7 ± 0.1 eV, indicating the possible existence of such a mechanism. Adsorption of a monolayer of SF₆ onto the Ru covered with a monolayer of oxygen shifts the F(ls) peak to lower binding energy by 0.8 eV. Similar effects due to oxygen have been observed previously in the physical adsorption of Xe on W(111).     

Contribution des moments octupolaire et hexadecapolaire a l'elargissement des raies spectrales de molecules linearaires

Expressions for linewidths due to hexadecapole-dipole, hexadecapole-quadrupole, hexadecapole-octupole, and hexadecapole-hexadecapole interactions have been determined from the Anderson-Tsao-Curnutte theory. We have shown—for linewidths of CO₂ with self-broadening and broadened by N₂, as well as for linewidths of CO with self-broadening and broadened by N₂, O₂, H₂, and CO₂—that allowance for octupolar and hexadecapolar mements yields improved agreement with experimental data for high |m|-values.     

Comparison of the first negative corona current pulses in N2 + SF6 and CO2 + SF6 mixtures

The current waveforms of the first negative corona pulses in a small point-to-plane gap have been measured with a nanosecond time resolution in N₂ + SF₆ and CO₂ + SF₆ mixtures at a pressure 50 kPa for various contents of SF₆ as a function of applied gap voltages. The physical mechanism for the pulses in these mixtures with low concentration of SF₆ has been described using the streamer-based theory. The influence of changing admixtures of SF₆ in N₂ and CO₂ has been compared. Differences in the pulse waveforms observed in N₂- and CO₂-based gas mixtures are explained by differences in the first and second Townsend ionization coefficients. This work was supported by the Grant Agency VEGA from the Ministry of Education of Slovak Republic under contracts 1/1011/04 and 1/2017/05.     

Continuous-wave CO2 laser spectroscopy of SF6, WF6, and UF6

The linear absorption of CO₂ laser radiation in SF₆, WF₆, and UF₆ has been measured by using optoacoustic detection techniques. Absolute absorption coefficients per Torr as low as 1 × 10^?7 cm^?1 Torr^?1 in a 2-cm active path length could be measured by taking advantage of calibration measurements performed with SF₆.     

Pressure-shock-controlled pulsed molecular beams

A method of controlling the duration of pulses of intense molecular beams is suggested. The idea of the method is the shortening of an initial molecular beam pulse by producing a pressure shock in front of a solid surface through which the beam passes. Experiments on shortening H₂, He, SF₆, SF₆/H₂(1/10), and SF₆/He(1/10) molecular beam pulses are reported. The parameters of the beams incident on, and transmitted through, the surface are studied. The gas density in the initial beam and in the pressure shock before the surface is estimated. The intensity and duration of shortened molecular pulses are found as a function of the initial intensity, angle of incidence, and the diameter of a hole on the surface through which the beam passes. It is established that the duration of the shortened beam decreases greatly with increasing incident intensity and decreasing hole diameter. It is shown that intense pulsed H₂, He, SF₆, SF₆/H₂(1/10), and SF₆/He(1/10) molecular beams with a pulse duration of ≤10–15 μs and an extent of ≤1–2 cm can be generated with the method suggested.