Half-width calculations for CO lines broadened by CO2

Half-widths of CO lines, in the fundamental and first overtone bands, broadened by CO₂ have been computed using the Anderson-Tsao-Curnutte theory. Comparison with the high-resolution measurements of Varanasi at 295°K shows excellent prediction of line widths by the theory. Comparison is also made between calculations including dipole-quadrupole and quadrupole-quadrupole interactions with those taking only the dominant quadrupole-quadrupole forces into account. Line widthd at 295°K range from 0.126417 cm^-1 atm^-1 fom m = 1 to 0.04397 cm^-1atm^-1 for m = 32, which corresponds to the asymptonic kinetic-theory value. Half-width computations are also presented at 200°K and 250°K appropriate for Martian and Venusian atmospheres, respectively.     

Penning ionization electron spectroscopy of CO,HCl, HBr and of triatomic molecules N2O,NO2, CO2, COS and CS2

The energy of electrons released in ionization of di- and triatomic molecules by He (2¹S, 2³S), Ne and Ar (³P_{0, 2}) metastable atoms was measured. Attention was concentrated on the determination of peak shifts and peak form in order to elucidate new features of the mechanism of ionization with respect to ionization of atoms. In ionization by He (2¹S) atoms, asymmetric peak forms and greater shifts towards lower electron energy were found than in ionization by He (2³S) atoms. A tentative explanation for peak shifts in terms of orientation of molecules during the collision and of molecular orbitals involved in ionization was proposed. Effects due to J values of metastable atoms and molecular ions were described. The ionization of electronegative molecules (NO₂) probably takes place already at large particle separation because of mixing with the X⁺ABC^? ionic state which, on recombination, ionizes into X + ABC⁺ + e.     

Measurements of the HCN ν3 band broadened by N2

N₂-broadened halfwidths have been measured for 51 absorption lines belonging to the ν₃ fundamental band of hydrogen cyanide (¹H¹²C¹⁴N) near 3311 cm^?1. The data were recorded at room temperature using a Fourier transform spectrometer with a nominal resolution of 0.06 cm^?1. A nonlinear least-squares spectral-fitting procedure was used to obtain both line intensities and collision-broadened halfwidths from scans recorded at several different pressures. The N₂-broadened halfwidths, determined for all lines with J ≤ 25 in both the P and R branches of the band, show the expected distribution with J for broadening by a nonpolar gas. The halfwidth values range from approximately 0.17 cm^?1 atm^?1 near the band center to 0.11 cm^?1 atm^?1 for high-J lines. The band intensity for the ν₃ fundamental derived from these measurements is 236.2 ± 9.5 cm^?2 atm^?1 at 296 K, and empirical coefficients for the vibration-rotation interaction F-factor were also determined.     

Atom-atom potential in rotational line broadening for molecular gases: Application to CO lines broadened by CO,N2, O2 and NO

Linewidths in CO-CO, CO-N₂, CO-C₂ and CO-NO collisions have been calculated using an improved potential for atom-atom interactions in addition to the first-order terms of the electrostatic interaction. The energy parameters characterizing the Lennard-Jones potential have been estimated previously from second virial coefficients. Overall agreement between calculated and experimental linewidths (particularly for CO-O₂ mixtures for which the electrostatic contributions are weak) is thus obtained without any adjustable parameters. It is concluded that the atom-atom potential describes the angular dependence of the short-range forces in molecular collisions fairly adequately.     

Photodissociation of N2F4 by a nanosecond CO2 laser pulse

Photodissociation of N₂F₄ by a strong nanosecond CO₂ laser pulse was studied by probing the interaction volume with both UV and IR beams. Up to 20% of the molecules were found to be dissociated into NF₂ during the first few nanoseconds following the passage of the pulse.     

Effect of He and N2 on pulsed operation of CO2 lasers

Addition of He to a CO₂ laser quenched much the saturation effect of the pulsed output to increase its pulse width and its peak power. It was also newly found that the discharge current of a CO₂:N₂ mixture was suppressed to give rise to laser emission only during its suppressed period.     

N2F4 as saturable absorber of CO2 laser radiation

Tetrafluorohydrazine induces passive Q switching in a continuous-wave CO₂ laser in both the P and R branches of the 10.4 μ system, showing comparable effectiveness on all the accessible lines. At higher pressures, this gas forces the laser to oscillate in the 9.3 μ system in non frequency-selective cavities.     

Mesure des largeurs et des deplacements des raies de la bande 0 → 2 de CO autoperturbe et perturbe par N2, O2, H2, HCl,NO et CO2

Linewidths of CO pressure-broadened by itself and by foreign gases have been measured in the 0 → 2 band. An experimental slit correction was used. The very small lineshifts of compressed CO have also been estimated using two different methods of measurement. An order-of-magnitude estimate is given for lineshifts due to foreign gases.     

Microwave linewidths of C2H4O perturbed by H2, N2, O2 and CO2

Microwave linewidths of C₂H₄O (κ = -0.41) broadened by H₂, N₂, O₂, and CO₂ and considering dipole-quadrupole interactions have been calculated using the Mehrotra-Boggs theory (1977). This theory accounts satisfactorily for observed linewidths     

Rotational CARS for simultaneous measurements of temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air diffusion flame

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has over the years demonstrated its strong potential to measure temperature and relative concentrations of major species in combustion. A recent work is the development and experimental validation of a CO₂ model for thermometry, in addition to our previous rotational CARS models for other molecules. In the present work, additional calibration measurements for relative CO₂/N₂ concentrations have been made in the temperature range 294-1246 K in standardized CO₂/N₂ mixtures. Following these calibration measurements, rotational CARS measurements were performed in a laminar CO/air diffusion flame stabilized on a Wolfhard-Parker burner. High-quality spectra were recorded from the fuel-rich region to the surrounding hot air in a lateral cross section of the flame. The spectra were evaluated to obtain simultaneous profiles of temperature and concentrations of all major species; N₂, O₂, CO, and CO₂. The potential for rotational CARS as a multi-species detection technique is discussed in relation to corresponding strategies for vibrational CARS.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

Simplified models for the temperature dependence of linewidths at elevated temperatures and applications to CO broadened by Ar and N2

The broadening coefficients for i.r. lines of CO perturbed by Ar are calculated in the temperature range 300–3500 K using the formalism previously developed by two of us (D.R. and J.B.). The results are compared with high-resolution spectroscopic measurements of shock-heated CO-Ar gas mixtures. A simplified model is proposed to describe the temperature dependence of the linewidths. The resulting model is applied to CO broadened by N₂ and the results are critically discussed.     

High-pressure disproportionation phases of CO2 and CO

First-principles enthalpy minimization simulations with target pressures suggest that dense-packed disproportionation phases of CO₂ and CO can be transformed from selected molecular precursors under hydrostatic compression. In transformations, electrons are pushed from oxygen to carbon atoms to form electronic disproportionation phases with their chemical formulas of C^?2O${}_2^{+}$ and C^?O⁺. Simulations indicate that the space packing properties of reactive groups in a molecular crystal precursor, including the orientation and the number of bonding partners of each reactive group, mainly control transformation bonding pathways. Phonon dispersion spectra and molecular dynamic simulations confirm the metastability of both electronic disproportionation phases under high pressures.     

Largeurs des raies spectrales de CO autoperturbe et perturbe par N2, O2, H2, HCI,NO et CO2

Linewidths of CO self-broadening and broadened by N₂, O₂, H₂, HCI, NO, and CO₂ have been calculated using different contributions in the intermolecular dispersion potential.The quadrupole moment of some perturbers has been determined by comparison between calculated and observed linewidths. The values obtained for the quadrupole moments may depend on the dispersion potential, especially when it is low (as is the case for N₂, O₂ and H₂). For CO-CO and CO-NO, the electrostatic interactions including the octupole moment yield good results for the linewidths for high |m|-values.     

Laser spectroscopy of ethylene with waveguide CO2 and N2O lasers

Fifty Doppler-broadened absorption lines of ethylene have been measured within large profiles CO₂ or N₂O lase lines. These laser lines are produced by a high pressure waveguide laser and have a full width between 200 and 900 MHz. Eleven absorption lines, the more intense ones, have been assigned to the ν₇ band of C₂H₄. The other absorption lines must belong to hot bands or to the ν₇ band of H₂¹²C¹³CH₂.     

Radiofrequency spectroscopy of AsH3 inside a CO2N2O laser cavity

The method of radiofrequency spectroscopy inside a CO₂N₂O laser cavity has been applied to the observation of pure nuclear quadrupole resonance, A₁-A₂ transitions and two-photon transitions of AsH₃. From the assignment of these transitions some coincidences between laser lines and Δk = 3 transitions in the ν₂ band and Δ|k ? l|; = 3 transitions in the ν₄ band have been assigned. The quadrupole coupling constant eqQ and its rotational dependence χ_J, χ_K and χ_d, and the spin-rotation constants C_N and C_K for the As nucleus have been determined for the ground state. The effective values of eqQ has been determined for the ν₂ and the ν₄ states.     

Carbon molecular sieves from PET for separations involving CH4, CO2, O2 and N2

Carbon molecular sieves (CMS) have been made for the first time from PET textile fibres by carbonisation and pore mouth narrowing using CVD of benzene. The diffusion of O₂, N₂, CO₂ and CH₄ in these materials, and also in the commercial CMS Takeda 3A, was studied. It was found that the best PET based CMS was obtained after 10 min CVD time and had adsorption capacities and rates of diffusion similar to those of the Takeda 3A.     

The role of CO in CO2 lasers

The population inversion in a CO₂-He glow discharge has been calculated, taking into account CO produced by dissociation in the discharge. The calculation was based on experimentally determined electron energy distributions and the measured effective relaxation constant of CO₂ (001). It is shown that the population inversion is negligible in the absence of CO.     

Detection of small N2O concentrations using a frequency doubled CO2 laser

A reliable procedure for remote high-accuracy laser detection of N₂O as one of the principal destroyers of the protective ozone layer of the Earth has been developed. The procedure is based on using a CO₂-laser system emitting efficiently in the 4.5 μm range. In this case lasing from isotopic modification ¹²C¹⁸O₂ of carbon dioxide with its subsequent frequency doubling by a nonlinear crystal is used. With the object of reducing the price the composition of the active medium (both for TEA laser and low-pressure longitudinal-discharge-excitation laser) has been optimized. New high-efficiency intracavity frequency doubling schemes based on nonlinear AgGaSe₂ crystals have been developed for CO₂-lasers of both types. Low concentrations of N₂O and concentrations of the principal background gases CO and H₂O have been measured under real atmosphere conditions with the aid of the lidar complex built around these lasers.