Gasdynamic cw CO2 laser

The principles of the physical processes in a high-power gasdynamic cw CO= laser are considered. An equation is derived for the output power, with account taken of the vibrational-nonequilibrium flow of the mixture through the nozzle and of the action of the optical resonator. A theory of the energy of the optical resonator used in the GDL is constructed. The corresponding models of the working medium in the section in which the gas flows through a supersonic nozzle and the optical resonator are presented. The efficiency of a resonator with a uniform field is calculated. The first experiments that have led to realization of the idea of the GDL are described. Experiments that have established for the first time that inactive absorption takes place in the amplifying medium of GDL based on combustion products are also described.Translated from Trudy Ordena Lenina Fizicheskogo Instituta im. P. N. Lebedeva, Vol. 3, pp. 50–114, 1979.     

Pressure effects in the kinetics of cw laser induced reactions

Rate constantsk and translational temperaturesT have been determined for the decompositions of ethyl acetate and perfluorocyclobutane at various pressures induced by a continuous (cw) CO₂ laser. Arrhenius plots give activation energies in good agreement with those reported for thermal rate constantsk ₁. The ratiosk/k ₁ become progressively larger than unity with decreasing reactant pressure, indicative of laser induced non-thermalization, but the values ofk/k _t appear to reach limiting values at low pressures, similar to effects reported elsewhere for CH₃CF₂Cl. Analysis of the data suggests important general features of vibrational-translational energy transfer in polyatomic compounds.     

Infrared multiphoton dissociation of13CF3Cl induced by CO2 laser pulses

Selective infrared multiphoton dissociation of¹³CF₃Cl induced by CO₂ laser pulses adjusted on = 1071.9 cm^–1 has been studied in the energy rangeE between 0.5 and 2 J per laser pulse or fluence range between 5 and 25 J per cm², and in the pressure range between 0.10 and 60 Torr. The effect of these parameters on the isotopic selectivity of the dissociation gives information on the rotational relaxation constants. As for the dissociation probabilities, they vary exponentially withE ^–1. The applicability of such an Arrhenius-type relation is discussed and semi-quantitatively justified.     

Application of a cw quantum cascade laser CO2 analyser to catalytic oxidation reaction monitoring

Catalytic oxidation reaction monitoring has been performed for the first time with a trace gas carbon dioxide analyser based on a continuous wave (cw), thermoelectrically cooled (TEC), distributed feedback (DFB) quantum cascade laser (QCL) operating at around 2307 cm^?1. The reaction kinetics for carbon monoxide oxidation over a platinum catalyst supported on yttria-stabilised zirconia were followed by the QCL CO₂ analyser and showed that it is a powerful new tool for measuring low reaction rates associated with low surface area model catalysts operating at atmospheric pressures. A detection limit was determined of 40 ppb (1 standard deviation) for a 0.1 s average and a residual absorption standard deviation of 1.9×10^?4.     

New cw optically pumped FIR emissions in HCOOH,D2CO and CD3Br

New FIR emissions lines have been observed for HCOOH, D₂CO and CD₃Br. Assignments have been made of the HCOOH lines and for most of those of CD₃Br. For D₂CO, most of the new emissions showed a corresponding cascade transition.     

Tunable simultaneous double-wavelength operation of a cw CO2 laser

Stable step-tunable simultaneous double-wavelength emission from any branch combination of the 9.6 and 10.6 μm bands of a cw CO₂ laser is reported in which the relative strengths of the two signals may be controlled.     

MJ and collision energy dependent attenuation of Rg (3P2) by CF3Br

The total attenuation cross-section of Rg (³P₂) (Rg = Ar, Kr) by the collision with CF₃Br is measured as a function of the magnetic sub level M_J of Rg (³P₂) and the collision energy. For Ar (³P₂), the attenuation process indicates a M_J dependence, in particular, the cross-section of the M_J = 0 state is lower compared with that for other states. On the other hand, Kr (³P₂) shows no M_J dependent attenuation.     

Synthesis of ethylamine with a cw tunable CO2 laser

The successful synthesis of ethylamine with a cw tunable CO₂ laser is reported. This action occurs at normal pressure (5.32×10⁴ Pa) and temperature (<100° C). No catalyst is used. The experiment shows a high directionality of this reaction. No other product except ethylamine is yielded. A possible mechanism for this reaction is discussed.     

Effect of rotational relaxation on the yield of the multiphoton dissociation of CF3Cl and CF3Br under TEA-CO2 laser pulses

The yield of the multiphoton dissociation of CF₃Cl and CF₃Br induced by TEA-CO₂ laser pulses has been studied in the pressure range between 0.25 and 8 Torr, the laser wavelength being chosen so as to excite preferentially the minor isotopic components¹³CF₃Cl and¹³CF₃Br. For both compounds the dissociation probability is found either to increase almost linearly or to decrease monotonously with gas pressure, according as the laser beam is focused or unfocused, respectively. This behaviour is explained by rotational relaxation effects, and a value of 22ns·Torr for the rotational self-relaxation time of CF₃Cl is obtained.     

Thermal desorption of CF3Br induced by resonant infrared absorption

A thin film of CF₃Br is condensed on a cold Ag or ZnSe surface (≈ 110 K) and is subsequently desorbed under resonant absorption of CW CO₂ laser radiation. The condensation process is determined by the surface temperature. The desorption is monitored as a transient pressure peak. The maximum desorption rate is proportional to the film thickness and to the resonantly absorbed infrared laser power. The desorption process is of thermal nature and determined by the thermal properties of the Ag or ZnSe substrate. The wavelength dependence varies strongly with surface temperature and film thickness.     

New cw fir laser emissions from CO2 laser-pumped vinyl bromide

47 new cw far-infrared laser lines with wavelenths between 453 and 2356 m have been obtained by optically pumping vinyl bromide (C₂H₃Br) by a CO₂ laser. A significant portion of these lines has wavelengths longer than 750 m.     

New FIR laser lines from CHD2OH optically pumped by a cw CO2 laser

This work reports 83 new optically pumped far infrared laser lines, using deuterated methyl alcohol, CHD₂OH, as active medium. For each line we list the measured wavelength, its polarization relative to the pump line, the optimum gas pressure and the CO₂ laser pump power at the maximum absorption.     

Further investigations on ir pumping of CH3OD and CD3OD by a cw CO2 laser

Respectively, 41 and 36 new cw far-infrared lasing lines have been observed using a waveguide resonator in CH₃OD and CD₃OD pumped by a low-pressure CO₂ laser emitting in the 9.4, 10.4 m regular bands and in the 10.8 m hot band. The wavelength range was 46.6 m–1.67 mm in CH₃OD and 53.6 m–1 mm in CD₃OD.     

Theoretical investigation on kinetics and thermochemistry of reaction of CHF2CF2OCH2CF3 with OH radicals and global warming potentials

Theoretical investigation has been carried out on the mechanism, kinetics and thermochemistry of the gas-phase reactions between CHF₂CF₂OCH₂CF₃ and OH radical using a new hybrid density functional M06-2X/6-31+G(d,p) and G2(MP2)//M06-2X/6-31+G(d,p) methods. The most stable conformer of CHF₂CF₂OCH₂CF₃ is considered in our study and the possible H-abstraction reaction channels are identified. Each reaction channel shows an indirect H-abstraction reaction mechanism via the formation of pre-reactive complex. The rate coefficients are determined for the first time over a wide range of temperature 250–1000 K. At 298 K, the calculated total rate coefficient of k_OH = 1.01×10^?14 cm³ molecule^?1 s^?1 is in good agreement with the experimental results. The heats of formation for CHF₂CF₂OCH₂CF₃ and CF₂CF₂OCH₂CF₃ and CHF₂CF₂OCHCF₃ radicals are estimated to be -1739.25, -1512.93 and -1523.94 kJ mol^?1, respectively. The bond dissociation energies of the two C-H bonds are C(-H)F₂CF₂OCH₂CF₃: 423.34 kJ mol^?1 and CHF₂CF₂OC(-H)HCF₃: 411.87 kJ mol^?1. The atmospheric lifetime of CHF₂CF₂OCH₂CF₃ is estimated to be around 4.5 years and the 100-year time horizon global warming potentials of CHF₂CF₂OCH₂CF₃ relative to CO₂ is estimated to be 601.     

Optoacoustic cross-section measurements for ir pulses: CO2 laser absorption by CF3I

The pulsed optoacoustic method is studied to measure absolute infrared multiphoton absorption cross sections. The influence of the thermalisation by the walls of the cell is shown to be very important at low pressure. This influence is analysed both experimentally and theoretically by solving the coupled diffusion and relaxation equations for vibrational and translational energies. The sensitivity of the method is limited by a spurious pressure signal present even with non-absorbing gases. This parasitic signal is attributed to an absorption located on the inner surface of the windows of the cell. For instance, using KCl windows, the observed spurious signal corresponds to about 10⁻⁴ of the total laser energy, transmitted from the windows to the gas. This proportion is independent on the energy fluence. Taking care of these limitations, we have measured the absorption cross section of CF₃I at the different wavelengths of the (001–020) transitions of the CO₂ laser. The typical energy fluences in these experiments were varied from 10⁻³ to 1J/cm². To be in collision free conditions, the CF₃I pressure was made equal to 0.2 Torr.     

A computer model of a transverse discharge cw CO laser

A kinetic model has been developed for the investigation of the novel performance of a CO laser, on which efficient extraction of laser power was obtained by exciting a subsonic gas mixture of CO/N₂/He/O₂ through transverse dc discharge. Kinetic equations for direct excitation by electron impact, V-V and V-R/T energy transfer, and stimulated emission are coupled with a semi-one-dimensional flow model. Careful consideration is devoted especially to the V-V transfer process of CO–N₂ and N₂–N₂. The laser power was calculated by a constant gain method. The laser output performance, examined as a function of gas mixture ratio, temperature, flow velocity, and discharge current, was in good agreement with the experiment.     

Vanadium oxidation as a result of cw CO2 laser irradiation in atmospheric air

New results are reported concerning the vanadium oxidation by cw CO₂ laser irradiation in air at atmospheric pressure. Particular emphasis is paid both to the initial stage and the development of the oxidation process under the action of the laser radiation. Some aspects are finally discussed concerning the quantitative theoretical interpretation of the experimentally recorded data.     

cw far-infrared lasing in15NH3, stark resonantly pumped by a CO2 or N2O laser

CF₂ClCF₂Cl and ethyl acetate have absorption bands of similar width centered at the same frequency. Kinetics of the decompositions of these compounds by a cw CO₂ laser have been studied over a range of laser frequencies extending to 25 cm^?1 below band center. At constant translational temperature and pressure, the CF₂ClCF₂Cl rate constant changes by more than 200 with frequency, while the corresponding change for ethyl acetate is at most 3. The effect of laser frequency increases with increasing CF₂ClCF₂Cl pressure, while the reverse is true in ethyl acetate. Arrhenius plots show activation energies independent of both frequency and pressure.     

Study of simultaneous oscillation on several transitions in cw CO laser

Received: 13 September 1995/Revised version: 5 August 1996