Infrared diode laser spectroscopic detection of CF2 carbene produced by CO2 laser photolysis of CHCLF2

Infrared diode laser spectroscopy was applied to the detection of CF₂ carbene produced by CO₂-laser-induced dissociation of CHClF₂. Time-resolved spectra of CF₂ in several rotation-vibration states were observed. The initial concentration of CF₂ was estimated to be 5 × 10¹⁶ molecules cm⁻¹ from an analysis of the time-resolved spectra. The effect of Ar diluent on the time variation of the concentration of CF₂ is discussed.     

Energy dependence of SF6 dissociation by pulsed CO2 laser radiation

The fractional dissociation,³²Γ, of ³²SF₆ by the output of a pulsed TEA CO₂ laser has been found to depend upon Φ, the total integrated laser intensity, as ³²Γ ∞ Φ^m for both the P(20) and P(16) laser lines, where m ≈ 3 in the range 2 < Φ < 7.2 J/cm² and increases from 3 to ≈ 4 as Φ is reduced from 2 to 0.9 J/cm².     

Chlorine isotope enrichment in CO2 TEA laser photolysis of CF2Cl2

A number of lines from a CO₂ TEA laser were used to photolyze CF₂Cl₂. Enrichment of the ³⁵Cl and ³⁷Cl isotopes in the molecular chlorine formed during the photolysis was observed using a mass spectrometer. Maximum enrichment was about 1.8. The dependence of enrichment on wavelength, reactant concentration, inert gas pressure, and the presence of SiF₄ is reported. Of particular interest is the persistence of significant enrichment at pressures up to several hundred torr (≈ 10⁵ Pa). Aside from the practical significance of this enrichment at high pressures, it suggests that there are important contributions from isotopically specific interactions after the laser pulse.     

32SF6 dissociation rate during irradiation by a tea CO2 laser

A new experimental method is presented for measuring the multiple-photon dissociation rate of SF₆. It appears that there is a reverse process which associates the photofragments into SF₆. The measured dependence of the dissociation probability versus laser flux seems to agree qualitatively with theoretical models.     

Surface modification of LDPE film by CO2 pulsed laser irradiation

The influence of the pulsed CO₂ laser irradiation on the surface structure of the LDPE film was investigated. Significant changes were observed on the surface of laser treated films as it was verified by the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy and contact angle-measurement. Formation of polar functional groups onto the LDPE surfaces exhibited by the ATR-FTIR spectra was shown to be strongly dependent on the number of the CO₂ laser pulses. The intensity of the polar groups increased with increasing the number of pulses up to two and then slightly decreased at three laser pulses. This was also confirmed with the contact angle measurements in which the sample subjected to two laser pulses showed the highest wettability i.e. the lowest water drop contact angle. The concentration of peroxide groups formed on the surface of the laser treated films was determined quantitatively by UV spectroscopic method using iodide procedure. The latter results showed a similar trend with the results obtained using FTIR spectroscopy.     

SF6-sensitized dissociation of UF6 with a pulsed CO2 laser

The dissociation of UF₆ sensitized by SF₆ excited with a pulsed CO₂ laser in the presence of H₂ and CO as scavengers has been investigated. In the SF₆-UF₆-H₂ system the dissociation yields have been determined as a function of the laser frequency, the fluence, and H₂ partial pressure. A maximum dissociation yield has been found at a laser frequency of 935 cm^?1. No obvious dissociation of UF₆ was observed in the UF₆-SF₆ system without F-atom scavengers.     

Sensitized multiphoton dissociation of UF6 IN SF6-UF6 mixtures by a tea CO2 laser

UF₆ undergoes decomposition in the presence of SF₆ when mixtures of both are irradiated with a TEA CO₂ laser. The mechanism for UF₆ decomposition may involve vibrational energy transfer from excited SF₆ and laser absorption from the same laser pulse by excited UF₆ in its vibrational quasi-continuum     

N2 laser pumped dye laser photolysis

An N₂ laser pumped dye laser has been used as the exciting pulse source in flash photolysis with a time resolution in the ns range. Using the apparatus described it was possible to monitor second order decays. Advantages of this set-up are tunability, reproducibility of the exciting source, and the rapidity of the measurements.     

Gas phase unimolecular decomposition and chemiluminescence of tetramethyldioxetane initiated by a tea CO2 laser

Time resolved chemiluminescence spectra of pure tetramethyldioxetane are obtained for the first time using pulsed infrared laser excitation. The only major product, acetone, is shown to be formed by at least two pathways: a unimolecular, collision free, decomposition and a collision induced mechanism. Spectral and temporal behaviour indicate that neither singlet nor triplet acetone are the primary products. Other possibilities are discussed.     

Time-resolved optical emission spectroscopic measurements of He plasma induced by a high-power CO2 pulsed laser

Laser-induced breakdown spectroscopy of helium plasma, initially at room temperature and pressures ranging from 12 to 101 kPa was investigated using a transverse excitation atmospheric CO₂ pulsed laser (λ = 9.621 and 10.591 μm, a full width at half maximum of 64 ns, and an intensity from 1.5 to 5.36 GW cm⁻²). The helium breakdown spectrum is mainly due to electronic relaxation of excited He, He⁺ and H. Plasma characteristics were examined in detail on the emission lines of He and He⁺ by the time-integrated and time-resolved optical emission spectroscopy technique. Optical breakdown threshold intensities, ionization degree and plasma temperatures were obtained. An auxiliary metal mesh target was used to analyze the temporal evolution of the species in the plasma. The results show a faster decay of the continuum emission and He⁺ species than in the case of neutral He atoms. The velocity and kinetic energy distributions for He and He⁺ species were obtained from time-of-flight measurements. Electron density in the laser-induced plasma was estimated from the analysis of spectral data at various times from the laser pulse incidence. Temporal evolution of electron density has been used for the estimation of the three-body electron-ion recombination rate constant.     

Multiphoton tea CO2 laser excitation of the triplet state of propynal

Multiple infrared photon excitation of propynal triplet molecules gives rise to a strongly perturbed phosphorescence. Following absorption of a few IR photons per molecule the phosphorescence spectrum extends to higher energy, the intensity increases, the decay — deviating from the original exponential decay — accelerates and the emission quantum yield drops dramatically. These findings are explained in terms of temperature sensitive radiative (T₁ → S₀) and radiationless (T₁ → S₀) processes with the vibrational temperature as the determining factor. During the perturbed triplet decay, the IR excitation initially confined to the vibrational degrees of freedom becomes distributed among all degrees of freedom which results in a decrease in the vibrational temperature and thus a complex phosphorescence decay.     

Dynamics of a CO chemical laser initiated by flash photolysis of CS2NO2

The time-resolved spectrum and small signal gain of CO laser emission obtained from flash photolysed CS₂NO₂ are reported and analysed. It is suggested that NO₂ efficiently quenches high vibrational levels of CO. A method is described for using the gain characteristics to estimate the quenching rates.     

Ultraviolet hot-band spectra using a CO2 laser

Application of an IR laser pulse to a UV absorbing system induces an optical density transient in the latter as the thermal population is redistributed. An IR/UV cross-beam spectrometer is described which generates a continuous plot of such thermally-induced optical density differences as the UV absorption wavelength is scanned.     

On the mechanism of intermode vibration-to-vibration energy transfer in CH3F excited by a tea CO2 laser

The v₃ mode of CH₃F was excited by irradiation with a TEA CO₂ laser pulse, and the time-resolved emission spectra of the v₃ overtone and the 3 μ;m region were observed. The results indicate that the population of the v₄ level behaves kinetically in the same manner as that of 2v₃ or 3v₃. This suggests an efficient energy transfer between these levels.     

Raman analysis of SF6 molecular beams excited by a cw CO2 laser

In a molecular beam the effects of vibrational pumping of SF₆ (ν₃ = 948 cm^?1) are studied, using a line-tunable cw CO₂ laser. Intracavity spontaneous Raman scattering is used for analysis. For excitation in the collision regime (x_E/D ≤ 1), a thermal redistribution of the ν₃ excitation over all vibrational modes is found, together with an average absorption up to six photons per molecule. The infrared absorption profile shows a red-shift of 6 cm^?1. For excitation in the relatively rare collision regime (x_E/D ? 4), a structured non-thermal ν₁ Raman spectrum is observed, especially in the case of seeded molecular beams (10% in He). The observed hot-band peaks can be explained in terms of single-photon absorptions and collision-induced near-resonant V-V energy transfer, leading to single, double and triple excitations of the ν₃ mode. The value of T_rot in the beam is found to influence sensitively the non-resonant energy-transfer rate [e.g. hν₃(948 cm^?1)+ΔE_rot → h(ν₄ + ν₆)(962 cm^?1) relative to the near-resonant transfer rate (hν₃ + hν₃ → 2hν₃ + 3.5 cm^?1)].     

CO2 laser induced reactions of trichloroethylene

The pressure and laser-power dependence of the product distributions in the TEA CO₂ laser induced decomposition of trichloroethylene were studied. At moderate pressures molecular elimination of HCl to give CClCCl via intermolecular energy transfer was found to be the major reaction path. At low pressures a pure laser-induced CCl bond fission to give CHCCl was found to be the primary, reaction step.     

Reductive carboxylation of alkyl halides with CO2 by use of photoinduced SmI2/Sm reduction system

Upon visible-light irradiation, reductive carboxylation of alkyl halides takes place by using a SmI₂/Sm mixed system under atmospheric CO₂ to afford the corresponding carboxylic acids in good to excellent yields.     

CO2 tea laser-induced photochemical enrichment of boron isotopes

Mixtures of BCl₃ and H₂S are irradiated with 10.55 μm radiation (P(16) line of the 001–100 band of CO₂) from a TEA laser. After several hours of irradiation it is found that the maximum ¹⁰B to ¹¹B ratio of recovered gaseous boron containing material (primarily unreacted BCl₃) is 0.413 ± 0.004. The corresponding ratio of the BCl₃ starting material is 0.242 ± 0.002. The ¹⁰B concentration has therefore been increased from 19.5% to 29.2%. Further, by irradiating similar mixtures with 10.18 μm radiation (R(30) line of the same CO₂ vibrational band) this ratio changes to 0.169 ± 0.002, the ¹⁰B concentration being lowered to 14.4%. All experiments are performed in a small static system and chemical procedures for recovering milligram quantities of BCl₃ selectively enriched in either isotope are described.     

Homogeneous decomposition of gaseous methanol induced by CO2 laser

The laser heating procedure has been used to study chain reactions under strictly homogeneous conditions. The rate constants for the initiation and overall chain decomposition of methanol have been determined.

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