Photoluminescence of O2 and S2 ions in synthetic sodalities

Photoluminescence spectra of oxygen-doped chloro- and bromosodalites and sulfur-doped chloro-, bromo- and iodosodalites were measured at temperatures between 4.2 and 300 °K. At 4.2 and 77 °K, the emission spectra of oxygen-doped sodalites consisted of a series of peaks in the wavelength range 400–700 nm, with an average energy separation of ∼ 1000 cm^-1. In addition, fine structure, attributed to lattice modes, was observed in each vibrational band. At 4.2 and 77 °K, the sulfur-doped samples showed a multiband spectrum in the 500–750 nm range, with an average separation of ∼ 570 cm^-1 between bands. The spectrum at 4.2 °K exhibited some asymmetry not observed at 77 °K, but no fine structure was resolved. At 300 °K weak, broad-band luminescence was observed from both oxygen- and sulfur-doped samples, with no vibrational structure evident. The results compared very favorably with those reported for oxygen- and sulfur-doped alkali halides, and by analogy the spectra were attributed to luminescence from O^-₂ and S^-₂ molecular ions.     

Absorption coefficients for hydrogen—II. Calculated pressure-induced H2–H2 vibrational absorption in the fundamental region

The coefficient for pressure-induced vibrational absorption in H₂ndash;H₂ collisions was calculated for temperatures from 298 to 7000°K and wave numbers between 100 and 40,000 cm⁻¹ for local thermodynamic equilibrium. Because only transitions with a net change of +1 vibrational quanta were considered, the absorption was centered near the fundamental at 4161 cm⁻¹ in the infrared. The model included electronic configuration interaction, mechanical anharmonicity, vibration-rotation interaction, excited vibrational states, and more realistic intermolecular potential and line shapes than previously used. The integrated absorption coefficient at 3000°K was 2.1 times the previous theoretical value. An approximate formula for the absorption coefficient is given for rapid calculation.     

氧化亚氮3000—0200和1001—0110跃迁带在高温下的线强度

采用乘积近似法计算了氧化亚氮分子的总配分函数，其中转动配分函数考虑了离心扭曲修正，振动配分函数采用谐振子近似. 利用计算所得的配分函数和实验振动跃迁矩平方及Herman-Wallis因子系数，计算了氧化亚氮3000—0200和1001—0110跃迁带在常温和高温下的线强度. 结果显示，当温度高达3000K时，计算所得线强度与实验值及HITRAN数据库提供的结果仍符合较好. 这表明高温下的分子配分函数和线强度的计算是可靠的. 还进一步计算了氧化亚氮3000—0200和1001—0110跃迁带在更高温度(40 关键词： 氧化亚氮 配分函数 线强度 高温     

Crystal growth of high magnetostrictive polycrystalline Fe81Ga19 alloys

High magnetostrictive Fe₈₁Ga₁₉ alloy was prepared by induction heating zone melting method. The microstructure, solute partition behaviour, orientation evolution and magnetostriction are investigated. During the crystal growth process, the initial small grains gradually grow into large columnar crystals, and the solid-liquid interface shows slightly concave morphology. The equilibrium solute partition coefficient (k₀), effective solute partition coefficient (k_e) and solution diffusion coefficient (D) are calculated to be 0.74, 0.76 and 1.04×10⁻⁹ m²/s, respectively. In the steady growth stage, the composition distribution of the FeGa rod is uniform with average level about 18.50 at% Ga, which is close to the nominal composition. The deviation of the 〈001〉 orientation from the axial direction evolves from about 8° to 3° along the growth direction, and the corresponding magnetostriction increases from the initial 180 ppm to the final 305 ppm.     

Fluctuation analysis of the29Si (d,p)30Si reaction at 1.1–2.1 MeV

The excitation functions of the²⁹Si(d, p)³⁰Si reaction in the deuteron energy range of 1·1–2·1 MeV have been measured in steps of 9.3 keV at angles 40°, 60°, 90°, 100°, 110°, 130° and 150° for the following groups of protons: p_o (g.s. of the³⁰Si nucleus), p₁ (2·23 MeV), p₂ (3·51 MeV), p_3,4 (3·77 and 3·79 MeV), p_5,6 (4·81 and 4·83 MeV), p₁₀ (5·48 MeV) and p_n (5.61 MeV). Within the framework of Ericson's theory of statistical fluctuations the autocorrelations, cross-angle correlations and cross-group correlations have been calculated and the mean coherence width of the³¹P compound nucleus has been deduced to be 27 keV.The authors would like to express their thanks to K. Putz for the efficient performance of the electronical equipment and to the staff of the Van de Graaff laboratory for operating the accelerator.     

Carbon dioxide activation and alkali compound formation. I. Vibrational characterization of oxalate intermediates

The activation of CO₂ in thin potassium layers adsorbed on Cu(1 1 1) has been studied with time-evolved Fourier transform-infrared reflection absorption spectroscopy. The growth of thin layers by reactive evaporation of potassium in a CO₂ atmosphere permits control of the K:CO₂ stoichiometry, which strongly affects the selectivity in the formation of intermediates and the decomposition pathways of the layer. Layers grown in a CO₂ rich atmosphere exhibit the preferential growth of stoichiometric potassium oxalate K₂C₂O₄ (D_2h). The molecular identity of oxalate with D_2h symmetry is confirmed by vibrational spectra utilizing isotopic substitution methods (¹³CO₂ and C¹⁸O₂) and by the use of isotopic mixtures of CO₂/C¹⁸O₂ and CO₂/¹³CO₂. A comparison of the isotope data with theoretical calculations gives an estimated OCO bond angle in oxalate of 132°. Far-IR spectra obtained with synchrotron radiation indicate the equivalent interaction of all oxygen atoms with the potassium. A comparison of the vibrational data with theoretical ab initio calculations confirms the structural model of an oxalate species that is bulk coordinated with no strong directional bonding and all oxygen atoms equally interacting with potassium.At medium and low CO₂:K ratios, very complex vibrational spectra are observed, indicating the formation of an oxalate surface species with C_2v symmetry in addition to D_2h⁻ oxalate, CO₂⁻ and CO₂²⁻ species.     

Raman spectroscopy of RuSr2(Eu1.5Ce0.5)Cu2O10 magneto-superconductor

Raman spectroscopy studies are reported for the RuSr₂Eu_1.5Ce_0.5Cu₂O₁₀ (Ru-1222) compound at various temperatures of 300, 250, 200 and 90 K. Three distinct vibrational bands: the first at 110, 140, and 160 cm⁻¹, the second at 295 and 347 cm⁻¹, and third one at 651 cm⁻¹ are seen in Raman spectra of the compound at room temperature. These bands are attached to the Cu atoms’ c-direction, the Ru atoms’ ab-plane stretching and Ru atoms’ c-direction anti-stretching modes. Below 200 K, an extra vibrational mode is also seen at 260 cm⁻¹. Also, with a decrease in temperature, though the Cu vibrational modes remain intact, the Ru atoms’ ab-plane stretching (295 cm⁻¹) and c-direction anti-stretching (651 cm⁻¹) modes shift gradually to higher wave number positions. The frequencies of modes at 260 and 651 cm⁻¹ showed anomalous softening and line-width broadening below 100 K that corroborates well with the spin ordering seen in susceptibility studies. The studied compound is a ferromagnetic superconductor with magnetic ordering of the Ru spins at 200 K and superconductivity below 30 K. A magnetic and electrical transport characterization of the compound is also presented briefly.     

Determination of relaxation times of N2 (v=1) level in presence of water vapor

The vibrational kinetics in CO₂-N₂-H₂O and CO-N₂-H₂O mixtures behind a reflected shock were investigated in the temperature range 500–1500°K by measurement of the intensity of the infrared emission of the gas. The vibrational relaxation time of nitrogen after collision with water molecules is obtained. The reasons for the disagreement of the presently available experimental data on the rate of this process are analyzed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 84–89, June, 1978.     

Application of CI expansion techniques to the computation of two-photon absorptivities

Summary We show how conventional linear expansion techniques for both electronic and vibrational wave functions can be used for the computation of matrix elements governing the two-photon absorption probability in molecules. In particular, the²Σ⁺ A←²∏X transition matrix elements of OH and the¹Σ _g ⁺ E,F←¹Σ _g ⁺ X of H₂are computed using 1) the sum over states in the Born-Oppenheimer approximation with inclusion of vibrational wave functions, 2) solution of perturbation theory equations by expansion in the CI basis at fixed nuclei, followed by a kind of vibrational averaging. The results are compared with experiment and discussed. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Electrical and infrared study of Bi2Sr2Ca1Cu2O8 in semiconducting, superconducting ceramic and superconducting glass ceramic state

We have studied the electrical and infrared properties of Bi₂Sr₂Ca₁Cu₂O₈ compound in three states. Electrical and IR measurements show that the pure powder state sample is a semiconductor, the ceramic Bi₂Sr₂Ca₁Cu₂O₈ sample prepared after annealing at 820°C for 240 hours shows a T_c of 85 K, whereas Bi₂Sr₂Ca₁Cu₂O₈ sample prepared through glassy route, i.e. melting at 1250°C and annealing at 820°C for 240 hours shows a drop of T_c by 5 K. The infrared spectra of superconducting ceramic and glass ceramic states in the available frequency range of measurement reveals the presence of three phonons. Since the vibrational mode around 595 cm^–1 is due to CuO₂ layers and as the CuO₂ layers are responsible for T_c in the ceramic superconductors, any change in these layers will affect the T_c. The shifting of the 595 cm^–1 mode towards lower frequencies in the glass ceramic due to different preparation process, indicates that there is a change in CuO₂ layers resulting in a change of T_c, which is confirmed by Four probe dc measurements.     

Laser schlieren measurement of vibrational relaxation times for N2O in mixtures containing CO,N2, and Ar behind a shock wave

The laser schlieren method has been used behind shock waves where the temperatures are 410–2400°K to measure the vibrational relaxation times for N₂O and also for mixtures of N₂O with CO, N₂, and Ar. The vibrational relaxational times of N₂O have been measured for collisions with these partners, and it has been found that the effectiveness of N₂ in relaxation is close to that of N₂O, whereas CO results in accelerated vibrational relaxation of N₂O. A comparison is made with the available published data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 3–8, November, 1984.We are indebted to V. V. Savkin for performing the mass spectral analyses.     

Line broadening and shift coefficients of acetylene at 1550 nm

Pressure broadening and shift coefficients have been measured for the ν₁ + ν₃ band of acetylene, C₂H₂, broadened by N₂, H₂, D₂, air, and the noble gases at 295 K. Coefficients are reported for lines between 6470 and 6612 cm⁻¹ (1512-1546 nm). The pressure broadening coefficients are in general agreement with those reported for other vibrational bands, indicating that they are insensitive to vibrational excitation. The pressure shift coefficients, by contrast, are found to differ substantially among vibrational bands.     

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.     

Intensity distribution in theA 2Π –X 2Σ+ system of Yttrium monoxide

The integrated intensities of a few bands in the vibrational structure of the astrophysically significant ‘orange’ system of the molecule yttrium monoxide, have been measured experimentally by the technique of photographic photometry. The effective vibrational temperatures of the source are found to be 2402±180 K and 2901±230 K for the subsystemsA ²Π_3/2−X ² Σ ⁺ andA ²Π_1/2−X ² Σ ⁺ respectively.     

ИЗМЕРЕНИЯ ЭЛЕКТРОННЫХ РЕЛАКСАЦИОННЫХ ПРОЦЕССОВ В МАРГАНЦЕВЫХ ФЕРРИТАХ

The measurements of magnetic loss factor in the system Mn _x Fe_3–x O_4+y for 0.62x1.66 are described. The temperature range used was 2°K to 360°K and four fixed frequencies 75, 150, 300, and 600 kHz were employed. The results show, that three distinct processes were found with various dependences upon composition. The corresponding maxima in tg vsT curves are situated at 2°K, 10°–50°K, and 90°–350°K respectively. The connection of these processes with electron transport and/or reorientation of distortions surrounding octahedrally coordinated Mn³⁺ ions is used as a basis for an interpretation already proposed earlier.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

Submillimeter-wave spectroscopy of HCN in excited vibrational states

Measurements of the rotational spectrum of HCN in excited vibrational states have been extended to higher-J values. The transitions reach J=8←7 around 710 GHz for most vibrational states studied in this investigation and J=22←21 near 2 THz for the (020) and (030) vibrational states. Using a pure sample of gaseous HCN at 350 K, selected states up to one quantum in the C–H stretching vibration at 3311.5 cm⁻¹ have been investigated. Even transitions having two quanta in the C–H stretch could be studied employing a glow discharge in a gas mixture of CH₄ and N₂. Molecular constants in 13 vibrational states have been obtained, several of which have been studied for the first time by rotational spectroscopy. The vibrational temperature in the discharge system is found to be about 1500 K for the stretching vibrational modes and about 600 K for the bending states.     

渐近非对称陀螺分子H122C16O的高温光谱

在直接计算分子配分函数的基础上,将无转动跃迁偶极矩平方近似为一常数,计算了渐近非对称陀螺分子H¹²₂C¹⁶O 100000-000000跃迁在中等温度和高温下的线强度. 计算结果在500K时与HITRAN数据库的结果吻合相当好.在温度高达3000K时与HITRAN数据库的结果仍符合较好,表明分子配分函数和线强度的高温计算是可靠的.在此基础上,进一步计算了渐近非对称陀螺分子H¹²₂C¹⁶O 100000-000000跃迁带在极端高温4000和5000K的线强度并报道其模拟光谱.计算结果对大气分子高温光谱的实验测量和理论研究均有一定的参考价值. 关键词： 高温光谱 渐近非对称陀螺分子 配分函数 甲醛     

ARC study of the oxygen Schumann-Runge system

Other investigations have shown that the Schumann-Runge system of oxygen is excited by an inverse predissociation mechanism, O + O→ O^*₂. Under the condition where this excitation mechanism dominates, there is some question as to whether the radiation yielded a true rotational/vibrational electronic band spectrum, as opposed to a recombination continuum. Furthermore, there is controversy as to whether the spectral intensity is that given by equilibrium theory. The present work utilized a 1 atm arc jet facility to heat air and O₂-noble gas mixtures to temperatures between 3000 and 3500°K. Both photographic and photoelectric spectra were recorded. In the latter case, wavelength scans from 2000 to 6000 Å were carried out with 5 Å resolution to obtain absolute intensity data. The spectra were found to have true rotational/vibrational electronic band structure, and were identified as the O₂ Schumann-Runge ssytem. Comparison with an equilibrium radiation model showed excellent agreement. A slight adjustment was made in the electronic transition moment for the NO(β) system as demanded by the air runs.