Selective dissociation of SF6 molecules in a two-frequency infrared laser field

The dissociation of SF₆ in the field of two infrared frequencies is studied. It is shown that the selectivity of dissociation is increased compared to the single frequency dissociation case. The dispersion characteristics of the vibrational quasicontinuum have been obtained. A theoretical model of the processes is discussed.     

Towards an explanation of collisionless multiple-photon laser dissociation of SF6

The rapidity and high degree of molecular vibrational excitation by the absorption of ir laser light in SF₆ and other molecules may be due in large part to the anharmonic splitting of excited vibrational states. Anharmonic splitting of an overtone or combination vibrational level (i) is possible only in molecules with degenerate vibrational states, (ii) can be comparable in magnitude to the net anharmonic shift of the level, (iii) is generally much larger than the rotational shifts which have previously been proposed as an explanation for the dissociation of SF₆. We find that consecutive nearly resonant transitions are possible in SF₆ up to υ₃ = 5 to 10.     

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.     

Selective multiphoton IR dissociation of SF6 molecules under nonequilibrium conditions of a pulsed gasodynamically cooled molecular flow interacting with a solid surface

The process of the isotope-selective multiphoton IR dissociation of SF₆ molecules under the non-equilibrium conditions of a pulsed gasodynamically cooled molecular flow interacting with a solid surface was experimentally studied. The SF₆ molecules dissociate as a result of excitation in a shock wave generated in the flow, in the flow incident onto the sold surface, and in an unperturbed flow (in the absence of the solid). The experiment was based on detecting the luminescence from HF^* molecules (λ ≈ 2.5) μm) accompanying the SF₆ dissociation in the presence of H₂ or CH₄, the emission intensity being a measure of the SF₆ dissociation yield. The molecular beam parameters were studied. The time-of-flight spectra of SF₆ in the flow interacting with the surface were measured under various experimental conditions. The spectral and energy characteristics of the SF₆ dissociation process were determined in the flow interacting with the solid surface and in the unperturbed flow. The dissociation product (SF₄) yield was measured and the coefficient of its enrichment with the ³⁴S isotope was determined. It is demonstrated that, using the shock wave formation, it is possible to increase the efficiency of the isotope-selective dissociation of SF₆ molecules. An explanation of the observed results is proposed. The gas density and temperature in the incident flow and in the shock wave were estimated. The results are analyzed and compared to the other published data on the SF₆ dissociation in a molecular beam.     

Study of the rates of collisional decay of population, orientation, and alignment by stimulated photon echo in a molecular gas

A stimulated photon echo technique with specially selected linear polarizations of the coherent resonant driver pulses is used to study depolarizing collisions in the molecular gas SF₆ and in mixtures of it with buffer He and Xe. The collisional decay rates of the population, orientation, and alignment in an ensemble of gas particles are determined for the first time in a single experiment. These relaxation rates are measured as a function of the longitudinal translational velocities of the resonant particles. To within the experimental accuracy, no significant dependence of the collisional decay rates on the translational velocities of the particles was observed. This result confirms the conventional theoretical approach to depolarizing collisions. In pure SF₆ the decay rates for the orientation and alignment were lower than the relaxation constant for collisions involving a change in the longitudinal velocity (elastic collisions) that is known from experimental observations of the ordinary photon echo. This means that only some of the elastic collisions participate in destroying the multipole moments of the levels. Evidence is found that the relaxation of the multipole moments created by polarized radiation in a resonant medium of molecular SF₆ gas depends on j, the total angular momentum of the level. Zh. éksp. Teor. Fiz. 113, 826–833 (March 1998)     

Energy and pressure dependence of the CO2 laser induced dissociation of sulfur hexafluoride

Low pressure SF₆ with its isotopes in natural abundance was irradiated by a pulsed CO₂ laser operated on theP20 line (10.6 μm band). Dissociation yields of³²SF₆ and³⁴SF₆ were measured separately. If the radiation is focussed into the cell, the dissociation yield is proportional to the 3/2 power of the laser energy, as was derived under general conditions and confirmed experimentally. The reaction probabilityP(Φ), the fraction of molecules dissociated by an energy flux Φ, was measured using parallel light. For both isotopes,P(Φ) saturates at high energy flux close toP=1. At a lower flux (2 J cm⁻²), the dissociation probability of³²SF₆ displays a threshold, whereas the dissociation probability of³⁴SF₆ is a very steep function of Φ over the whole range of fluxes.P(Φ) at the higher energy flux was measured in a cavity absorption cell, in which up to 80% of the molecules were dissociated by a single pulse. Below 0.2 mbar SF₆ the dissociation yields for both isotopes are pressure independent. Above 2 mbar the isotopic selectivity is completely lost. Addition of hydrogen always decreases the dissociation yields.     

The spectral structure of the low level excitation in the process of the collisionless dissociation of polyatomic molecules

The resonant characteristics of the energy absorbed by SF₆ gas which is deeply cooled and exposed to IR laser irradiation of moderate intensity have been investigated experimentally. It was found that the gas cooling changes the dependence of the absorbed energy on the laser intensity and allows to reveal the structure of the spectrum. The experimental results are explained by a dominating influence of the two-photon absorption on the excitation of low vibrational levels in the laser fields of moderate intensity.     

Growth of van der Waals clusters in steady supersonic Laval nozzle flow: change in number density of SF6 monomers undergoing clustering

A mixture of SF₆ (4% molar fraction) and inert Ar gas was continuously fed into a plane-symmetric guided Laval nozzle. The clustering of SF₆ was observed using an FT-IR spectrometer in the nozzle flow (optical pathlength: 10 mm). The density and vibrational temperature of the SF₆ monomers were experimentally determined from the absorption peaks of the monomers. We theoretically calculated the density of the SF₆ monomers as a function of distance from the throat of the nozzle using a cluster formation model based on the RRK (Rice–Ramsperger–Kassel) theory to represent the dynamics of dissociation of the vibrationally excited clusters. We found that the model adequately simulated the decrease in SF₆ monomers and 10 collisions of the vibrationally excited SF₆ clusters with Ar atoms were necessary for the stabilization of the clusters under our experimental conditions. Received: 20 June 2000 / Revised version: 26 October 2000 / Published online: 21 February 2001     

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.     

Threshold behavior of multiple photon dissociation of SF6

Multiple photon dissociation of SF₆ by a short pulse of a CO₂ laser has been investigated by simultaneous measurements of the average number of photons absorbed per molecule 〈n〉 and chemiluminescence intensities which result from the dissociated F atoms. A criterion for the dissociation threshold which is independent of laser wavelength is found to be 〈n〉 = 16 ± 3 photons per molecule. A thermal distribution of the excited molecules is shown to be inconsistent with the behavior just above threshold.     

IR absorption of highly vibrationally excited SF6

In a double-resonance experiment, the absorption of various CO₂ laser lines by sulfur hexafluoride was measured, before and after the SF₆ was pumped by a fixed frequency CO₂ laser to a level of 5 quanta/molecule. The absorption is substantially shifted to longer wavelengths. But the short wavelength wing of the absorption band is not completely bleached. Instead a shoulder of several cm⁻¹ width is left. This shoulder is probably important for the explanation of the infrared laser induced dissociation of SF₆.     

Optoacoustic investigation of the mechanisms in the infrared optogalvanic effect

Simultaneous observations of the optogalvanic and optoacoustic effects were performed in CO₂, NH₃ and SF₆ discharges under irradiation by resonant infrared 10 μm laser radiation. The dependence of the galvanic and acoustic signals on the discharge current, and their time evolution following a switch of the laser radiation were investigated. The observations proved that the infrared optogalvanic effect occurs through two different mechanisms, a gas kinetic temperature dependence of the discharge parameters and a modification of the pion production through the vibrational molecular excitation.     

The effect of magnetic stress and stiffness modulus on resonant characteristics of Ni-Mn-Ga ferromagnetic shape memory alloy actuators

The prospect of using ferromagnetic shape memory alloys (FSMAs) is promising for a resonant actuator that requires large strain output and a drive frequency below 1 kHz. In this investigation, three FSMA actuators, equipped with tetragonal off-stoichiometric Ni₂MnGa single crystals, were developed to study their frequency response and resonant characteristics. The first actuator, labeled as A1, was constructed with low-k bias springs and one Ni-Mn-Ga single crystal. The second actuator, labeled as A2, was constructed with high-k bias springs and one Ni-Mn-Ga crystal. The third actuator, labeled as A3, was constructed with high-k bias springs and two Ni-Mn-Ga crystals connected in parallel. The three actuators were magnetically driven over the frequency range of 10 Hz-1 kHz under 2 and 3.5 kOe magnetic-field amplitudes. The field amplitude of 2 kOe is insufficient to generate significant strain output from all three actuators; the maximum magnetic-field-induced strain (MFIS) at resonance is 2%. The resonant MFIS output improves to 5% under 3.5-kOe amplitude. The frequency responses of all three actuators show a strong effect of the spring k constant and the Ni-Mn-Ga modulus stiffness on the resonant frequencies. The resonant frequency of the Ni-Mn-Ga actuator was raised from 450 to 650 Hz by increasing bias spring k constant and/or the number of Ni-Mn-Ga crystals. The higher number of the Ni-Mn-Ga crystals not only increases the magnetic force output but also raises the total stiffness of the actuator resulting in a higher resonant frequency. The effective modulus of the Ni-Mn-Ga is calculated from the measured resonant frequencies using the mass-spring equation; the calculated modulus values for the three actuators fall in the range of 50-60 MPa. The calculated effective modulus appears to be close to the average modulus value between the low twinning modulus and high elastic modulus of the untwined Ni-Mn-Ga crystal.     

The geometric structure of pure SF6 and mixed Ar/SF6 clusters investigated by core level photoelectron spectroscopy

The S 2p core level photoelectron spectra of Sulphurhexafluoride clusters have been investigated together with heterogeneous Ar/SF₆ clusters, created by doping Ar host clusters (with a mean size of 3600 atoms) with the molecule. Surface and bulk features are resolved both in the argon 2p and the sulphur 2p core level photoelectron spectra. For the latter level such features were only observed in the pure cluster case; a single feature characterizes the S 2p core level spectra of SF₆ doped argon clusters. From the chemical shifts, investigated with respect to SF₆ doping pressure. It can be concluded that the host clusters get smaller with increasing doping pressures and that the SF₆ molecules predominantly stay below the cluster surface, whereas the Argon core stays intact. We have neither observed features corresponding to SF₆ on the cluster surface, nor features corresponding to molecules deep inside the bulk in any of the spectra from the pick-up experiments.     

Photolysis of SF6 adsorbed on Si(111)-7 × 7 by monochromatic soft X-ray

Continuous-time photoelectron spectroscopy (PES) and photon-exposure-dependent photon-stimulated desorption (PSD) were employed to investigate the monochromatic soft X-ray-induced dissociation of SF₆ molecules adsorbed on Si(111)-7 × 7 at 30 K (SF₆ dose = 3.4 × 10¹³ molecules/cm², ～ 0.5 monolayer). The photon-induced evolution of adsorbed SF₆ was monitored at photon energies of 98 and 120 eV [near the Si(2p) edge], and sequential valence-level PES spectra made it possible to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are ～ 2.7 × 10^? 17 and ～ 3.7 × 10^?17 cm², respectively. The changes in the F^? and F⁺ PSD ion yields were also measured during irradiation of 120 eV photons. The photon-exposure dependencies of the F^? and F⁺ ion yields show the characteristics: (a) the dissociation of adsorbed SF₆ molecules is ascribable to the substrate-mediated dissociations [dissociative attachment (DA) and dipolar dissociation (DD) induced by the photoelectrons emitting from the silicon substrate]; (b) at early stages of photolysis, the F^? yield is mainly due to DA and DD of the adsorbed SF₆ molecules, while at high photon exposure the F^? formation by electron capture of the F⁺ ion is likely to be the dominant mechanism; (c) the F⁺ ion desorption is associated with the bond breaking of the surface SiF species; (d) the surface SiF is formed by reaction of the surface Si atom with the fluorine atom or F^? ion produced by scission of S–F bond of SF_n (n = 1–6) species.     

The fluorescence and IR energy deposition from from CO2 laser irradiation of SF6−H2 mixtures

The multiple photon excitation and dissociation of SF₆ and hydrogen mixtures is measured by using simultaneously pulsed optoacoustic detection to monitor the energy deposition and time resolved HF fluorescence to monitor the production of vibrationally hot HF. From these studies we deduce that at least three mechanisms lead to production of vibrationally excited HF. One mechanism produces free F from the unimolecular laser-induced decomposition of SF₆. The second mechanism involves the reaction between two vibrationally hot SF₆ molecules to produce free F. In both of these cases the F atom subsequently react with H₂ to produce vibrationally hot HF. The third involves the reaction between a vibrationally hot SF₆ molecule and a hydrogen molecule producing vibrationally hot HF directly.     

Transformation of resonant Raman scattering into luminescence in CdxZn1−xTe mixed crystals: Time-resolved spectroscopy

We report an experimental study of time characteristics of secondary emission in Cd_xZn_1-xTe mixed crystals (x = 0.32) under resonant excitation with a picosecond dye laser. When the incident laser frequency is tuned on to the luminescence maximum of localized excitons, the decay curve of the intensity of “Raman-like” lines exhibits a single exponential decay. Off resonance, however, a short-lived component corresponding to Raman scattering appears in addition to the long-lived component. The intensity of the Raman component relative to that of the luminescence component increases with increase of the off-resonance frequency. From these temporal behaviors, we have found, for the first time, the transformation of resonant Raman scattering into luminescence in mixed crystals as a function of incident frequencies.     

Muonic X-ray intensities in SF6 and in H2+SF6

With a high pressure gas target muonic F and S X-ray intensities in SF₆ and H₂+SF₆ have been measured. It was found that the distribution of muons between sulphur and fluorine is not at all equal to the ratio of the atomic numbers Z.     

Multiple photon excitation of the v2 + v6 combination band of SF6 in a bulk and in a pulsed free jet

Multiple photon excitation of the v₂ + v₆ combination band of SF₆ in a bulk at T ≈ 295 K and cooled in a pulsed free jet up to T_V ≈ 160 K and T_R ≈ 40 K by a pulsed TEA CO₂ laser has been investigated. Obtained results are compared with the data on the v₃ vibration excitation. At exciting energy fluences ø = 0.1?2.5 J cm^-2 the levels in the region of the discrete vibrational states (v=3?5) are found mainly to be excited. Multiphoton absorption spectra at room temperature have a sharp resonant structure. The fraction of interacting molecules is considerably (3–7 times) less compared than that for the case of v₃ vibration excitation. Multiphoton absorption of the v₂ + v₆ and v₃ vibrations of SF₆ is shown to be proportional to the dipole moments of the corresponding transitions.     

Field distribution effects in laser driven diffusion through metal capillaries

A new approach for the IR laser driven diffusion through metal capillaries is reported in this paper. It reveals the influence of the inner distribution of the electromagnetic field on the resonant character of the diffusion of a mixture of SF₆ (resonant) and N₂ through an Ni capillary under IR irradiation. A waveguide model is proposed for the considered e.m. field-heterogeneous system interaction, an explanation for the persistence of the selective effects even at total pressures as high as 7 Torr being provided. Some spectral differences between the inside-capillary molecules and bulk-phase molecules are pointed out using a simple attenuation measurement method.