Reactions of molybdenum atoms with NO,O<Subscript>2</Subscript>, N<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript> molecules behind shock waves

Experimental results on the interaction of Mo atoms with various oxygen-containing molecules (NO, O₂, N₂O, and CO₂) at high temperatures (>1200 K) are presented, which are in close agreement with measurements at moderate and low temperatures. It is demonstrated that the height of the activation barrier is additionally increased for spin-forbidden reactions and that an increase in the heat of reaction causes an increase in the rate constant for a given type of reaction. For the reactions of Mo atoms with O₂ and N₂O, interpolated temperature dependences of the rate constants, based on the high-temperature measurements conducted in the present work and the published low-temperature data, are proposed.     

Inelastic collisions of slow electrons with SrBr<Subscript>2</Subscript> molecules

Inelastic collisions of slow electrons with SrBr₂ molecules were studied experimentally. The dissociative excitation cross sections of two lines of the strontium atom and eight lines of the singly charged strontium ion were measured. Six optical excitation functions were recorded over the electron energy range 0–100 eV. Dissociative excitation cross sections were also measured for two strontium monobromide sequences related to the B ²Σ⁺-X ²Σ⁺ system.     

Computer calculations for thermal behavior of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> melt

The thermal behavior of Na₂CO₃+Li₂CO₃ melt is studied by the method of thermodynamic simulation. The equilibrium compositions of the gas and salt phases are calculated at different temperatures in the initial argon atmosphere. Basic trends of the variation in the compositions of the melts and the gas phase above the melts in the presence of carbon are determined. The obtained results characterizing the stability of carbonate components in the melt are analyzed.     

Processes of dissociative excitation in collisions of electrons with CaI<Subscript>2</Subscript> molecules

The dissociative excitation of calcium atoms and ions and calcium monoiodide in e-CaI₂ collisions was studied by the method of extended crossing beams. The excitation cross sections of calcium atoms and ions in electron-atom and electron-molecule collisions are compared. The main channels of the reactions at low electron energies are discussed.     

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.     

Absorption by CS<Subscript>2</Subscript> molecules on “hot” band emission lines from a TEA CO<Subscript>2</Subscript> laser

We have measured absorption of emission from a TEA CO₂ laser, lasing on hot band lines, in pure CS₂ and a mixture of CS₂ with air, and we have determined the optimal lines for optical excitation. Numerical modeling has shown that as the peak intensity of the pump radiation is increased, we observe absorption saturation, the extent of which decreases as the pressure increases. The major factor responsible for absorption saturation is the “rotational bottleneck” effect. Depending on the peak intensity of the radiation, addition of a buffer gas can lead to an increase or decrease in the absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 61–66, January–February, 2007.     

Accuracy in determination of the temperature and partial pressure of CO<Subscript>2</Subscript> in CO<Subscript>2</Subscript>:N<Subscript>2</Subscript>:H<Subscript>2</Subscript>O:NO<Subscript>2</Subscript> mixtures by multiple-frequency laser probing

We present the results of analysis of the errors introduced by hot-band transitions 11¹0-01¹1, 03¹0-01¹1, 12⁰0-12⁰1 of the CO₂ molecule and the absorption lines of the H₂O and NO₂ molecules in determination of the temperature and partial pressure of CO₂, included in the gas mixture CO₂: N₂:H₂O: NO₂ at atmospheric pressure, by multiple-frequency laser probing using a CO₂ laser tunable over the lines of the 00⁰1-[10⁰0,02⁰0]_I,II ground-state laser transitions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 810–815, November–December, 2007.     

Rotational excitation of NH<Subscript>3</Subscript> and ND<Subscript>3</Subscript> due to He atom collisions

Quantum close-coupling and coupled-states approximation scattering calculations for rotational energy transfer of rotationally excited NH₃ and ND₃ due to collisions with He are presented. Calculations were performed for collision energies between 10^-5 and 10 000 cm^-1 using the NH₃-He potential of Hodges and Wheatley [J. Chem. Phys. 114, 8836 (2001)]. State-to-state and total quenching cross sections from some selected initial states are presented. Rate coefficients for ortho-NH₃ for the quenching 10+→00+ transition were obtained on potentials scaled to reproduce measurements of second virial coefficients with the results showing strong sensitivity to the potential, especially at low temperatures. Significant isotope effects are found in quenching cross sections in the cold to ultracold regime particularly in the region dominated by quasi-bound resonances, ~0.1 to 10 cm^-1. As ammonia has been translationally cooled via Stark deceleration methods, it is a good candidate for experimental study of such effects at cold temperatures. Comparison of rate coefficients with available theoretical results are also presented.     

Molecular Simulation of H<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, and CH<Subscript>4</Subscript> Adsorption in Coal Micropores

Based on the chemical model of coal, slit micropores with different pore sizes are established and structures are optimized in the software of materials studio. As the temperature rises, absolute adsorption capacities of H₂O are slightly affected, while absolute adsorption capacities of CO₂ and CH₄ gradually decrease. As the fugacity rises, excess adsorption curves of CO₂ experience increase-decrease-gentle three stages, while the curves of CH₄ gradually decrease. With the increase of pore size, adsorption capacities of H₂O increase, while adsorption capacities of CO₂ and CH₄ gradually decrease. H₂O firstly adsorbs on the oxygen-containing functional group, so the walls of pore are the preferential area for H₂O, while CO₂ and CH₄ choose to adsorb on–C–C–, therefore the walls are the primary area for CO₂ and CH₄. Strong potential in micropores and hydrogen bond among water molecules will promote the water adsorption, while the adsorptions of CO₂ and CH₄ are only induced by the Van der Waals interaction, but the difference between adsorption density and bulk density of CO₂ and CH₄ decides the change of excess adsorption capacity.     

The dissociative excitation of singlet and quintet nickel atom states in e-NiBr<Subscript>2</Subscript> collisions

The dissociative excitation of singlet and quintet nickel atom states in e-NiBr₂ collisions was studied by the method of extended intersecting beams. Optical excitation functions over the electron energy range 0–100 eV were recorded for most of the spectral lines observed. Possible dissociative excitation channels at low electron energies were discussed. The cross sections of dissociative and direct excitations and dissociative excitations of the NiBr₂ and NiCl₂ molecules were compared.     

Luminescence excitation in reactive molecular CO + O<Subscript>2</Subscript> collisions on the surface of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Eu

It is shown that the CO + O₂ → CO₂ catalytic reaction on the surface of Y₂O₃-Eu may lead to electronic excitation of Eu³⁺ luminescence centers due to the chemical energy release. The luminescence observed allows one to study the interaction between molecular particles of ultralow (thermal) energies with surface by optical methods.     

Self-modulation lasing regimes in a fast-flow CO<Subscript>2</Subscript> laser

Numerical simulation of self-modulation lasing regimes has been carried out for a CO₂ laser with transverse flow of the active medium through an unstable resonator with inhomogeneous internal pumping. Two types of steady-state self-modulation oscillation differing in the feedback mechanism were observed. The type of lasing regime and the conditions of its realization depend both upon the pumping profile and upon the composition and pressure of the working mixture, which makes it generally possible to control temporal characteristics of lasing.     

Measurement of the <Superscript>13</Superscript>CO<Subscript>2</Subscript>/<Superscript>12</Superscript>CO<Subscript>2</Subscript> concentration ratio in exhaled air by diode laser spectroscopy

A method for determining the relative concentration of ¹³C/₁₂C isotopes by the vibrational-rotational spectrum of CO₂ molecule absorption in the range near 2 μm was proposed. The use of the entire region of the diode laser tuning (∼7 cm⁻¹) and multivariate linear regression for spectrum approximation allow measurements at atmospheric pressure. The laser frequency is additionally stabilized by injection current variation. The ultimate sensitivity of the setup, determined by the plot of the squared Alan variance, is 0.03% for 2-min signal acquisition. The system does not contain elements cooled by liquid nitrogen and can be used in medical diagnostics.     

Oxidation of hydrogen sulfide and corrosion of stainless steel in gas mixtures containing H<Subscript>2</Subscript>S,O<Subscript>2</Subscript>, H<Subscript>2</Subscript>O,and CO<Subscript>2</Subscript>

The composition of volatile and solid products of oxidation of hydrogen sulfide and stainless steel in gas mixtures containing H₂S, O₂, H₂O, and CO₂ has been determined using mass spectrometry, x-ray diffraction analysis, and scanning electron microscopy. It has been shown that holding an H₂S–O₂ mixture at 301 K results in prevailing formation of elemental sulfur and iron sulfides in the form of porous hygroscopic crust on the reactor wall surface. Formation of gas-phase sulfur causes self-acceleration of the oxidation of hydrogen sulfide; the resulting water triggers corrosion of the reactor wall. Heating of the resulting sulfur-sulfide crust in O₂ medium is accompanied by formation of SO₂ and heat release at T > 508 K. After heating of the H₂S–CO₂ mixture to 615 K, H₂ and COS were found in the volatile reactants; no noticeable corrosion of the reactor wall has been detected. It has been established that addition of O₂ to the H₂S–CO₂ mixture and its heating to 673 K leads to formation of ferrous sulfates. The mechanisms of the observed processes are discussed.     

Graphite gasification in high-temperature gas flows containing H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript>

The rates of graphite gasification in interaction with high-temperature gas flows were compared. Carbon dioxide and a mixture of water vapor and argon taken in a 1:1 molar ratio were used as reagents. The reactor was a tube furnace; its temperature was varied from 1250 to 1400 K. The rates of graphite gasification in CO₂ and water vapor-argon mixture flows were approximately equal at 1250–1300 K, whereas, at 1350–1400 K, the water vapor-argon mixture exhibited higher reactivity than CO₂. The data obtained were approximated by Arrhenius dependences; the activation energy was found to be 153 kJ/mol for CO₂ and 248 kJ/mol for H₂O-Ar.     

Luminescence in collisions of low-energy ions with graphite and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Excitation of H⁺, H₂ ⁺, H₃ ⁺, He⁺, and Ar⁺ ions by impact on graphite and Al₂O₃ was investigated by means of emission spectroscopy in the 50–1000 eV energy range of the projectiles. Emission of Balmer series from excited neutral hydrogen is observed for both targets. In addition, for the Al₂O₃ target a continuum emission is observed. The continuum probably originates from excited M_nO_m molecules produced in the collision cascade, when surface atoms bound by ionic bonds are released after the bond breaking caused by neutralization. The spectra obtained under Ar⁺ -bombardment show Ar II lines emitted by backscattered ions.     

Properties of powders produced by evaporating CeO<Subscript>2</Subscript>/Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> targets exposed to pulsed-periodic radiation of a CO<Subscript>2</Subscript> laser

The characteristics (phase composition, grain shape, grain size distribution, and specific surface area) of Ce_0.78Gd_0.22O_2-δ nanopowders produced by exposing the target to pulsed CO₂ laser radiation are reported. Reasons for a threefold increase in the output of the experimental powder-preparation unit (up to 60 g/h) with the characteristic grain size (≈10 nm) remaining unchanged are discussed.     

Microstructure and superconducting properties of the DyBaCuO ceramic doped with Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>, NaCl,and KClO<Subscript>3</Subscript>

This paper reports on a study of the effect of doping with Na₂CO₃, NaCl, and KClO₃ salts on the microstructure and superconducting characteristics of ceramics with nominal compositions Dy_{1 ? x} M _x Ba₂Cu_{3 ? y} O_{7 ? δ} and DyBa₂Cu_{3 ? y} O_{7 ? δ} : M _x for M = Na, K; x = 0.2, 0.3, and y = 0, 0.2. The microstructure was characterized by transmission electron microscopy with local energy-dispersive x-ray in situ analysis (probe size ～1 nm). An analysis shows that none of the doping elements (Na, K, or Cl) enters into 123 grains in sizable amounts and that, as a result, the critical temperature of the superconducting transition remains practically constant in the range 90.0–93.5 K. Potassium and chlorine segregate at grain boundaries. It is shown that grain-boundary segregation of chlorine leads to a substantial increase in the superconducting critical current (by a factor 3–5 at 70 K) as compared to the undoped sample. The possible mechanisms accounting for the effect of Cl on intergrain critical current are discussed.     

Efficient and widely step-tunable terahertz generation with a dual-wavelength CO<Subscript>2</Subscript> laser

Coherent terahertz radiation in a widely step-tunable range of 72.3–2706 μm (0.11–4.15 THz) has been generated in GaAs crystal by difference-frequency generation using one CO₂ laser with dual-wavelength output. The peak power of THz pulse reaches 35 W at the wavelength of 236.3 μm, which corresponds to a pulse energy of 2.1 μJ. An average power of 10 μW has been achieved when working repetitively. This efficient terahertz radiation source is more compact and widely tunable than other THz sources pumped by CO₂ laser.     

Polarizability of two interacting molecules N<Subscript>2</Subscript> and O<Subscript>2</Subscript>

In the context of the Silberstein theory, by introducing model atoms, the polarizability of pairs of interacting molecules N₂-N₂, O₂-O₂, and N₂-O₂ was studied in relation to the mutual orientation and the intermolecular distance of the molecules in the pairs. The polarizability tensor for the equilibrium configurations of the (N₂)₂ and (O₂)₂ dimers was calculated.