Infrared diode laser spectroscopy of FCO: The ν1 and ν2 bands

The ν₁ (CO stretching) and ν₂ (CF stretching) bands of the FCO radical were observed with Doppler-limited resolution by an infrared diode laser spectrometer with Zeeman and source modulation. The FCO radical was generated by a 60-Hz discharge in one of the following three gas mixtures: O₂ + C₂F₄, CO + SF₆, and CO + C₂F₄, all diluted with He. The observed spectra were analyzed to determine the rotational constants, the centrifugal distortion constants, and the spin-rotation interaction constants. The band origins, 1861.6372(1) and 1026.1283(1) cm^?1 [with standard errors in parentheses], which were obtained, were found to agree well with matrix data, 1857 and 1023 cm^?1, respectively. The assignment of the observed spectra to the FCO radical was further supported by observing the ν₁ band of F¹³CO, which was obtained from ¹³CO and SF₆. The molecular structure and the force field of FCO are briefly discussed by using molecular constants obtained from the observed spectra.     

The effects of surface terminal bonds and microstructure of SiO2 aerogel films on dry etching

The effects of microstructure and surface terminal bonds of SiO₂ aerogel films on dry etching were investigated using Ar, SF₆, and C₂F₆ plasma gases. With Ar plasma etching, physical effect of ion bombardment on porous film was found. In residue-free SF₆ plasma etching, reactive etchant transport and high-mass ion bombardment were observed. With C₂F₆ plasma etching, fluorocarbon residue layer was revealed to maintain surface morphology as acting a barrier to radical transport and ion bombardment. An etching of 450°C-annealed SiO₂ aerogel showed that a dense surface induced the decrease in reaction area, inhibition of etchant transport, and then uniform etching.     

Electron energy distribution function in a hollow-cathode glow discharge in mixtures of nitrogen with electronegative gases

The electron energy distribution function (EEDF) in a hollow-cathode glow discharge in mixtures of nitrogen with electronegative gases is investigated. It is shown that small admixtures of SF₆ or CCl₄ to nitrogen significantly increase the number of electrons in the energy range 2–6 eV, which corresponds to the inverse part of the EEDF. In nitrogen with small admixtures of F₂ or NF₃, the EEDF differ slightly from that calculated for pure nitrogen. The EEDF in these mixtures substantially depends on electron attachment to electronegative gas molecules.     

Influence of short-and long-range interaction forces on the efficiency of collisional vibrational energy transfer in the vibrational quasi-continuum

Based on measurements of the time-resolved delayed fluorescence, the influence of universal interactions on the collisional vibrational energy transfer is studied in mixtures of vibrationally excited polyatomic molecules (acetophenone, benzophenone, and anthraquinone) with inert bath gases (Ar, C₂H₄, SF₆, CCl₄, and C₅H₁₂). From the dependences of the decay rates of delayed fluorescence on bath gas pressure, the efficiencies of the establishment of vibrational (V-V relaxation) and thermal (V-T relaxation) equilibrium after excitation of molecules into the vibrational quasi-continuum of a triplet state are estimated. The main emphasis is on studying the dependences of the efficiency of collisional vibrational energy transfer on temperature and the molecular characteristics of collision partners. It is found that the efficiency increases with the complication of the structure of bath gases for the V-V process and decreases upon the increasing of their mass for the V-T process. For the temperature range 273–553 K, the negative temperature dependence of the V-V transfer probability and the positive (Landau-Teller) dependence of the V-T transfer probability were obtained. It is concluded that the above regularities reflect the dominant role of long-range attractive forces in initiating the quasi-resonant V-V transfer and of short-range repulsive forces in the V-T transfer of vibrational energy.     

Photoabsorption cross sections for chlorinated methanes and ethanes between 46 and 100 Å

Photoabsorption cross sections for the methanes CCl₄, CCl₃F, CCl₂F₂, CClF₃, CF₄, CHClF₂, CHCl₂F and the ethanes C₂F₆, C₂ClF₅, C₂Cl₂F₄ were measured between 46 and 100 Å. In particular, the 0.2 Å resolution provides some insight into the Cl 2p absorption process. It is noted that the molecular cross section for all 8 Cl-containing gases display an L edge “discontinuity” of 3.55±0.15 Mb per Cl atom. The experimental molecular cross sections are compared with sums of atomic cross sections at 100 Å using both theoretical and empirical atomic values. The sums of theoretical atomic cross sections describe every experimental molecular value to better than 10%. The sums of empirical atomic cross sections describe molecular values to within 2%.     

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 ^? .     

Buffer gas pressure shift in the mF = 0 → mF = 0 ground state hyperfine line in Cs

The pressure shift of the m_F:0 → 0 microwave transition of the cesium ground state has been measured for seven buffer gases (He, Ne, N₂, CH₄, C₂H₆, C₃H₈, C₄H₁₀). The high resolution of the experimental apparatus (about one part in 10¹¹ also allows an accurate measurement of the temperature dependence of the shift.     

A KrF fast discharge laser in mixtures containing NF3, N2F4 or SF6

A fast discharge KrF laser system (λ = 248.5 nm) has been operated at 25 mJ/pulse, 3.0 MW peak power in high pressure He: Kr: fluoride mixtures containing low concentrations of both krypton and the fluorine donors N₂F₄, NF₃ and SF₆. Lasing action is reported for the first time in N₂F₄ and SF₆ with optimum energy output at 750 and 160 mJ/l respectively.     

Photon echo and stimulated photon echo study of various collisional-relaxation channels

Collisional relaxation in SF₆ gas and its mixtures with He and Xe is studied by photon echo and stimulated photon echo methods from the standpoint of the possibility of identifying the contributions of different types of collisions. The nonexponential nature of the kinetic curve of the photon echo is clearly observed for pure SF₆, it is weaker in the mixture SF₆+Xe, and it is virtually completely absent for high degrees of dilution of SF₆ with helium. These features can be explained on the basis of estimates, made from experimental data, of the critical delay between the exciting pulses (for which the nonexponential behavior should be most strongly manifested). In pure SF₆ it is possible to distinguish the contribution of the inelastic channel (rotational relaxation) and the contribution of weak collisions. To distinguish successfully the relaxation channels in mixtures with buffer gases a heavier buffer gas and a much better time resolution must be used. It is shown that data obtained on the orientation and alignment relaxation rates by the stimulated photon echo method can serve as an upper limit for the rates of inelastic processes which cannot be measured by the photon echo method. The combined use of photon echo and stimulated photon echo methods made it possible to obtain data on the cross sections for elastic and inelastic scattering of the collisional pairs SF₆–SF₆, SF₆–Xe, and SF₆–He. Zh. éksp. Teor. Fiz. 116, 47–56 (July 1999)     

Effect of collisions on the resonance vibrational polarizability of gaseous SF<Subscript>6</Subscript> and CF<Subscript>4</Subscript> molecules

The density dependences of the absorption cross sections and refractivity are experimentally studied for the SF₆ and CF₄ molecules in pure gases in the region of their ν₃ infrared vibrational-rotational antisymmetric modes. The dispersions of the refractive index are determined for both compounds by the Kramers-Kronig transformation of the spectral data obtained, and, for the SF₆ isotopomers, they are also measured by the method of two-color interferometry. Strong nonlinear dependences of optical parameters and their dispersions on the gas density are observed. The values of second optical virial coefficient B _R (ν) obtained for pure SF₆ are more than an order of magnitude greater than the values found earlier for mixtures of SF₆ with buffer rare gases. The results of calculations of the second virial coefficients of the absorption cross section and refractivity in terms of the DID model of interacting dipoles are in agreement with the experimental data in the band wings. Correlations between the behavior of the spectral dependence of functions B _R (ν) and the parameters of model intermolecular potentials used in the calculations are found.     

Cross relaxation in the rotational inversion doublets of ammonia in the far infrared

The effect of cross relaxation due to inelastic collisions on the inversion doublets of ammonia in the far infrared was studied by interferometric spectroscopy. Line widths and cross-relaxation rates were measured for several rotational transitions, using CH₂ = CF₂, C₂H₆, CF₄ and SF₆ as perturbing gases in the pressure range from 1 to 17.5 atm. The J-dependence of the observed cross-relaxation rates was calculated using a first Born approximation.     

Theoretical study on the interaction of heptafluoro-iso-butyronitrile decomposition products with Al (1 1 1)

Seeking environmentally friendly gas-insulated medium has become a research hotspot in recent years. At present, C₃F₇CN (Heptafluoro-iso-butyronitrile) is considered to be a potential SF₆ environment-friendly alternative gas and some achievements have been made in the study of its insulation and decomposition characteristics, but there are few reports on the compatibility between its characteristic decomposition products and materials. The investigation of compatibility between gas-insulated medium and material is an important part of evaluating its comprehensive performance. In this paper, we investigated the interaction between C₂F₅CN, CF₃CN, COF₂ and CF₄ with the aluminium widely used in electrical equipment. It was found that the interaction between C₂F₅CN, CF₃CN and Al (1 1 1) surface is strong. There are obvious charge transfer and electron orbital overlap between the C atom, N atom in CN group and Al (1 1 1). The interaction between COF₂, CF₄ and Al (1 1 1) surface is weak and van der Waal’s forces play the major role. Relevant results reveal the characteristics of C₃F₇CN decomposition products and provide theoretical guidance for evaluating the material compatibility between C₃F₇CN decomposition products and aluminium.     

From quantum chemistry to dissociation kinetics: what we need to know †

The relationship between rate constants for dissociation and the reverse association reactions and their potential energy surfaces is illustrated. The reaction systems e^? + SF₆ ? SF₆ ^? →SF₅ ^? + F, H + CH₃ ?CH₄, 2 CF₂ ? C₂F₄, H + O₂ →HO₂, HO + O ?HO₂ ? H + O₂, and C + HO →CHO are chosen as representative examples. The necessity to know precise thermochemical data is emphasised. The interplay between attractive and anisotropic components of the potentials influences the rate constants. Spin–orbit and electronic–rotational coupling in reactions between electronic open-shell radicals so far generally has been neglected, but is shown to have a marked influence on low temperature rate constants.     

HF-laser performance of CO2-laser-ignited mixtures of SF6 :H2 and of S2F10 :H2

We have used a CO₂ laser to ignite mixtures of SF₆ :H₂ and S₂F₁₀ :H₂. We observed HF lasing from these mixtures when an optical resonator was constructed around the reaction cell. The HF-lasing performance of the two mixtures was compared as a function of mixture ratio, fluorine-donor pressure, and CO₂-laser frequency. Under comparable conditions, the HF-laser output for S₂F₁₀ :H₂ mixtures was typically 5–6 times greater than that for SF₆ :H₂ mixtures. Spectral output of the HF laser was coarsely resolved to provide data about the vibrational and rotational states of the HF molecule.     

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.     

Emission characteristics of an ultraviolet emitter based on mixtures of krypton with low-aggressive halogen carriers pumped by a barrier discharge

The emission characteristics of a pulse-periodic excilamp with three dielectric barriers based on the 222-nm KrCl(X-B) and 248-nm KrF(X-B) emission bands have been investigated. The working gases of the lamp were mixtures of krypton with low-aggressivity halogen carriers (SF₆, CCl₄). Optimal compositions of Kr-SF₆ and Kr-CCl₄ mixtures for obtaining the maximum intensity of the system of 222-nm KrCl(X-B) and 248-nm KrF(X-B) bands have been determined. The results of lamp optimization depending on the parameters of the source of pulse-periodic short-duration barrier discharge are presented.     

The viscosity and diffusion coefficients of eighteen binary gaseous systems

The paper reports accurate measurements of the viscosity of the eighteen binary gaseous systems: CF₄ with He, Ne, Ar, N₂, CO₂, CH₄; SF₆ with He, Ne, Ar, N₂, CO₂, CH₄, CF₄ and O₂ with He, Ne, CO₂, CF₄, SF₆. The measurements were performed in a high-precision oscillating-disk viscometer at atmospheric pressure and in the temperature range 25–200°C for the systems containing CH₄ or SF₆ and in the temperature range 25–400°C for the remainder. The reported viscosities are believed to be accurate to within ±0.1% at room temperature and to within ±0.2% at 400°C.It is shown that the data conform to the extended law of corresponding states developed by Kestin, Ro and Wakeham despite the complexity of some of the component gases. The standard deviation between the experimental values and those calculated from the law of corresponding states is only 0.3% which is commensurate with the uncertainty in the experimental results.Binary diffusion coefficients derived from the mixture viscosity data are also presented; they have an estimated uncertainty of ±2%.     

Importance of pre-ionisation for the non-chain discharge-pumped HF laser

The importance of pre-ionisation for the non-chain discharge-pumped HF laser is studied through experiments on an X-ray photo-triggered laser using mixtures of Ne, SF₆, and ethane. The discharge dynamic in Ne/SF₆ mixtures or pure SF₆, as well as the stabilisation effect induced by C₂H₆ and consequences for the laser performance, are investigated for pre-ionisation electron density values, n_eo, ranging from 10⁶ cm^-3 up to 10⁹ cm^-3, as well as for the so-called discharge self-breakdown mode. Without ethane, the minimum n_eo value which is needed to complete 100% homogeneous charge deposition in the plasma is a very sharply increasing function of the SF₆ pressure. This hinders performance optimisation when the molecule used to react with F-atoms, for instance H₂, has no effect on the discharge dynamic. The minimum ethane partial pressure that is needed to stabilise the discharge depends on n_eo, the pumping pulse duration, the deposited electric charge, and the SF₆ pressure. Discharges in Ne/SF₆ can be much more efficiently stabilised by addition of a small amount of ethane than by an increase of n_eo. A pre-ionisation density as low as 10⁶ cm^-3 is sufficient to achieve the maximum laser energy value, but total suppression of the pre-ionisation has a detrimental effect on the active medium homogeneity. Received: 30 May 2000 / Revised version: 9 October 2000 / Published online: 9 February 2001     

Multiexponential decay of negative molecular ions as a result of target molecule distribution over vibrational states

The lifetimes of long-lived negative molecular ions SF₆⁻-, C₆H₅NO₂⁻, and C₆F₆⁻ are measured with a static mass spectrometer. A great spread in published data for the lifetimes of these ions is explained using a concept of multiexponential decay of molecular ions. The influence of the Boltzmann distribution of neutral target molecules over vibrational states on the lifetime of negative molecular ions is studied in terms of the Illenberger-Smirnov-Kompaneits simple statistical model. It is shown that this distribution has a profound effect on the multiexponential decay of molecular anions and, as a consequence, on the lifetime of negative molecular ions measured on different mass spectrometers.