Study of the absorption characteristics of molecular oxygen in the Schumann-Runge system at high temperatures: I. Calculations of absorption spectra

A program for calculating the absorption and emission spectra of diatomic molecules that can take into account the vibrational-rotational interaction and nonequilibrium conditions of the gaseous medium is created. The program also allows one to perform calculations for a particular experimental setup by specifying the corresponding instrumental function. The absorption cross sections of molecular oxygen are calculated in the Schumann-Runge system for the temperature range 1000–6000 K and the wavelength interval 130–280 nm. These calculations are compared with the experimental data obtained behind the shock wave front in oxygen-argon mixture at different temperatures for a number of wavelengths in the range of 160–270 nm.     

Determination of absorption cross sections for oxygen molecules in the Schumann-Runge band region at high temperatures

We have measured the absorption cross sections of oxygen molecules in oxygen and in an oxygen-argon mixture heated by a shock wave, in the wavelength range 190–250 nm at temperatures of 1500–7000 K, for thermal equilibrium conditions behind the shock wave front. Analysis of the absorption cross sections obtained allowed us to select a data set that adequately describes the absorption characteristics of the electronic transition X³Σ _g ⁻ → B³Σ _u ⁻ for the oxygen molecule. In order to approximate the temperature dependence of these cross sections at a temperature of 1500–4500 K, we chose the function σ(λ, T) = σ₀(λ)(1 − exp (−θ/T)) exp (− n*θ/T) where θ₀ = 1.4·10⁻¹⁷, 1.4·10⁻¹⁷, 1.2·10^{− 17}, and 1.3·10⁻¹⁷ cm², n* = 3.1, 4.1, 5.6, and 7.47 for wavelengths 190, 210, 230, and 250 nm, respectively; θ = 2240 K is the characteristic temperature of the O₂ molecules. The approximation error was 19–25% and did not exceed the experimental error. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 13–17, January–February, 2006.     

Study of oxygen vacancy ordering in mullite at high temperatures

High temperature X-ray diffraction and quenching experiments of mullite single crystals with Al₂O₃:SiO₂ ratio 2:1 have been performed to investigate the stability of the oxygen vacancy ordering close to the melting point of mullite. The experiments show that the structure of mullite exhibits an extremely stable, temperature-independent incommensurate modulation. Inspection of satellite reflections at different temperatures leads to the conclusion that the ordering scheme of oxygen vacancies after the crystallization of mullite persists to the melting point and does not show any disordering effects. The experimental results are in agreement with former theoretical calculations using a statistical mechanics approach which yield the critical temperature T_c > 3000°C.     

Broad-linewidth laser absorption measurements of oxygen between 211 and 235 nm at high temperatures

Absorption coefficient data are presented for molecular oxygen at temperatures between 1100 and 2000 K and discrete wavelengths between 211 and 235 nm. Measurements were made behind reflected shock waves using broad-linewidth ultraviolet laser radiation generated from a frequency-quadrupled, tunable, pulsed Ti:Sapphire laser. Test mixtures consisting of 15% O₂, 15% He and balance Ar were used to minimize the influence of vibrational relaxation on the reflected shock temperature. The experimental results are in good agreement with theoretical calculations and confirm that discrete features from the Schumann–Runge system dominate between 211 and 235 nm at temperatures higher than 1100 K.     

Infrared absorption of interstitial oxygen in silicon at low temperatures

Localized modes of oxygen incorporated interstitially in the silicon lattice are the origin of infrared absorption lines in the wavelength region between 29 and 1750 cm^–1. The occupancy of the excited states of the lowest energy normal mode of this center determines the relative strength of absorption lines of the highest energy mode in a band around 1136 cm^–1 at low temperatures. The ratio of the strength of the different lines can be used as an intrinsic thermometer of the system. Exact knowledge of this temperature then allows the precise determination of the concentration of interstitial oxygen with high sensitivity.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Predissociation and the vibrational spectrum of molecular oxygen in an intense laser field. A Schumann-Runge band interval

The probabilities of predissociation and vibronic transitions between the states of the oxygen molecule in the Schumann-Runge band in the presence of a strong laser field are examined. The interaction of the molecule with the laser field is described using the rotating wave approximation. The predissociation probabilities for the avoided crossing of two adiabatic molecular terms are calculated within the framework of the Landau-Zener model. The energies of the vibrational states in the laser field are determined by diagonalization of the adiabatic Hamiltonian in the harmonic oscillator basis set. The predissociation thresholds are determined and the Franck-Condon factors are calculated as functions of the frequency and intensity of the external electromagnetic field.     

分子筛在真空低温下水汽吸附脱附性实验研究

空间遥感仪器红外通道的信号衰减,入轨初期的主要原因是由于材料释放的水汽在低温光学窗口表面沉积,导致红外透射率降低所致。主动吸附是控制低温沉积污染的措施之一。分子筛对包括水汽在内的多种污染物具有良好的吸附作用,可以作为控制污染物的吸附材料。目前对于分子筛吸附特性的研究集中在常压环境。通过试验测试了13x型分子筛在高真空低温环境下,对水汽的吸附特性。     

Interaction of oxygen and carbon impurities with the multiphonon infrared absorption bands of Silicon at low temperatures

Infrared absorptance measurements of polycrystalline silicon and single crystals of silicon having oxygen and carbon impurities were carried out at low temperatures in the wavelength range of multiphonon infrared absorption of silicon. Peak absorptance and frequencies were measured at temperatures from 10 to 130 K at intervals of 10 K. Absorptance-temperature curves were plotted for multiphonon bands and impurity bands. It has been observed that the three phonon band [2 TO (Γ) + TA (L)] exhibits a resonance-like behaviour with the anti-stretching mode of Si-O at low temperatures.     

Experimentally determined oscillator strengths and linewidths for the Schumann-Runge band system of molecular oxygen—II. The (2-0) to (5-0) bands

Experimental oscillator strengths and predissociation linewidths have been measured at room temperature for the (2-0) to (5-0) Schumann-Runge bands of molecular oxygen using the Adelaide 6 m vacuum ultraviolet monochromator operated at a resolution of about 0.06 Å. Photoelectric detectors were used to measure the ultraviolet absorption at normally two different gas pressures for 37 groups of rotational lines, and the resulting data were interpreted using an equivalent width type of analysis. The variation with N″ of the oscillator strengths within each band was found to be smaller than that measured earlier for the higher vibrational bands. Measured oscillator strengths agree well with previously accepted values except for the (3-0) band, while the linewidths of the present work agree well with recent theoretical values for the (3-0) and (4-0) bands but are larger for the (2-0) and (5-0) bands. A modification was performed on the parameters of a recent theoretical predissociation model to produce excellent overall agreement between experimental and theoretical linewidths from ν' = 2 to 14. The present work provides results which can be used to construct accurate synthetic absorption profiles for studies of the atmospheric absorption of ultraviolet radiation by the Schumann-Runge bands.     

Theory of pressure-induced vibrational and rotational absorption of diatomic molecules at high temperatures

A derivation is given for the integrated absorption coefficient of pressure-induced pure rotational and vibrational transitions in binary collisions of homonuclear diatomic molecules of the same chemical species. The previously neglected effects of excited vibrational states, mechanical anharmonicity, and vibration-rotation interaction are taken into account to obtain more accurate absorption coefficients at high temperatures. In the region of the fundamental wave number the excited vibrational states make more of a contribution to the absorption than their relative population would lead one to expect.     

Measurements of near-UV absorption spectra of acetone and 3-pentanone at high temperatures

Gas phase acetone and 3-pentanone absorption cross sections have been measured in shock-heated gases in the wavelength range from 220 to 340 nm (the n−π^* system) at temperatures between 300 and 1100 K. Absorption measurements using a deuterium source and a kinetic spectrograph enable accurate, broadband measurements of absorption cross sections while simultaneously observing decomposition at elevated temperatures, thus minimizing errors due to product formation. The absorption spectra of both ketones increase in strength and shift to the red with increasing temperature. The spectra are fitted to a parameterized Gaussian curve to allow for calculations of the cross sections as a function of temperature and wavelength.     

Theory of pressure-induced vibrational and rotational absorption of diatomic molecules colliding with atoms at high temperatures

A derivation is given for the integrated absorption coefficient of pressure-induced pure rotational and vibrational transitions in binary collisions of homonuclear diatomic molecules with neutral atoms. The previously neglected effects of excited vibrational states, mechanical anharmonicity, vibration-rotation interaction, transverse components of the dipole moment, and a higher order term in the expansion of the z component of the dipole moment are taken into account to obtain more accurate absorption coefficients at temperatures above 423 K. In the region of the fundamental wave number the excited vibrational states make more of a contribution to the absorption than their relative populations would indicate.     

Magnetic susceptibility of intermetallic compounds in the Er-In system at high temperatures

The temperature dependence of the magnetic susceptibility (T) of intermetallic compounds of Er with In in a wide temperature range from 20 to 1600°C inherent in the solid state and melting process of the materials under review was studied for the first time by the Faraday method. For all test compounds, the temperature dependence was found to be approximated by the Curie-Weiss linear law both in a solid and liquid state. The Curie paramagnetic temperature, Curie-Weiss constants, and effective magnetic moment numbers per Er atom were calculated by computer processing of the ^–1(T) data, using the least-squares technique. A semiempirical estimation of the indirect exchange interaction parameter showed the test compounds to be characterized by exchange interactions of the Ruderman-Kittel-Kasuya-Yosida type.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 7–10, December 2004     

Optical characteristics of light-emitting diodes with high transparent conductive film at low temperatures

In this paper, we report the synthesis and transmittance of a titanium–indium–tin oxide (TITO) film, fabricated through a low-temperature process. The TITO film was fabricated by incorporating a 2-nm-thick titanium barrier at the bottom of an ITO film. The transmittance characteristics of the TITO film were examined for light-emitting diodes (LEDs) of various wavelengths at different post-annealing temperatures. A saturated high transmittance was observed at a temperature of 550 °C, which is relatively low when compared to that in the case of a conventional ITO film. Photoluminescence studies demonstrated that a 450-nm-thick TITO film, fabricated at 550 °C, was highly effective in improving the performance of the LED, when compared to conventional ITO films. The X-ray diffraction peaks, scanning electron microscopy images, and transmittance electron microscopy images confirmed that titanium atoms could improve the crystallization of ITO. It was found that non-crystallization in ITO was effectively activated by the titanium barrier. Furthermore, the optical bandgap (3.77 eV for the conventional ITO film) was improved to 3.92 eV in the TITO film. An infrared LED fabricated with a TITO film displayed 70% higher light output power than that with a conventional ITO film. These results suggest that using a titanium barrier is essential to effectively improve inactive nucleation sites in ITO films grown at low temperatures.     

Comparison between Si(100) and Si(111) in the reaction with oxygen at high temperatures

In this Letter, both the dynamics and kinetics of the reaction of oxygen molecules on Si(100)p2 × 1 and Si(111)7 × 7 and 1× 1 surfaces are compared. In all three cases, two distinct adsorption channels were observed. For oxygen molecules with translational energies less than 0.08 eV, the initial sticking is not sensitive to the energy or the angle of incidence, but displays a high sensitivity to the surface structure. At higher energies, a second channel becomes effective. The initial sticking coefficient increases rapidly and scales with the normal component of the translational energy, but the dependence on surface structure is greatly diminished. The kinetics of SiO formation are qualitatively similar on all surfaces with slightly higher rates on Si(111).     

Double-sided laser heating system at HPCAT for in situ x-ray diffraction at high pressures and high temperatures

An overview of a YLF:Nd laser heating system at the undulator x-ray diffraction station (16ID-B) of the high-pressure collaborative access team (HPCAT) of the Advanced Photon Source is presented. Based on the double-sided laser heating technique, the system is designed with considerable effort on the mechanical and optical stabilities, features for user-friendly operation, and the capability of accommodating diamond anvil cells of various heights up to 68?mm. This system has been used for x-ray diffraction studies of a wide range of materials to over 150?GPa and above 3000?K. Applying the laser heating technique to radial x-ray diffraction studies at simultaneous high-pressure and high-temperature (PT) conditions requires heating to be conducted at variable angles relative to the x-ray direction. A rotation laser heating design is discussed.     

Laser-heating diamond anvil cell studies of simple molecular systems at high pressures and temperatures

We report the application of new laser-heating techniques and sample preparation procedures for simple molecular materials (diatomic molecules and water) under high pressure in the diamond anvil cell (DAC). Both continuous and pulsed laser heating was employed. We probed the materials using Raman spectroscopy and also by analyzing the time evolution of the temperature of the metallic coupler that is used to absorb laser radiation and heat the sample. Raman measurements of H₂, D₂, N₂, H₂O and O₂ show a broadening of intramolecular vibrations at high P−T conditions, indicating a decreasing molecular lifetime, and hence suggest an increasing molecular dissociation. In diatomic molecules the intramolecular bonding can be further probed by observations of sidebands corresponding to vibrational transitions from excited states; the energies of these sidebands imply intramolecular potentials that become increasingly less anharmonic as pressure is increased. We also show that the pulsed heating technique combined with instantaneous radiative temperature measurements provides a useful tool for studies of thermochemical properties and phase transformation boundaries.     

Phase relations in the Fe-P system at high pressures and temperatures from ab initio computations

ABSTRACT

Based on the first-principles calculations within the density functional theory and crystal structure prediction algorithms iron phosphide phases stable under pressure of the Earth’s core and temperatures up to 4000?K were determined. A new low-temperature modification FeP-P2₁/c stable above ～75?GPa was predicted. Fe₂P with the allabogdanite structure has been established to be stable in the low-temperature region at ambient conditions. At 750?K it transforms into the barringerite structure. The transition from Fe₃P with schreibersite structure to Fe₃P-Cmcm was observed at 27?GPa, and the phase transition boundary is nearly isobaric. Fe₂P and FeP are thermodynamically stable at the Earth’s inner core pressures and 0?K according to the obtained results, whereas Fe₃P stabilizes with respect to decomposition to Fe?+?Fe₂P at high temperatures above ～3200?K.