H2-broadening,shifting and mixing coefficients of the doublets in the ν2 and ν4 bands of PH3 at room temperature

The broadening, shifting and mixing coefficients of the doublet spectral lines in the ν₂ and ν₄ bands of PH₃ perturbed by H₂ have been determined at room temperature. Indeed, the collisional spectroscopic parameters: intensities, line widths, line shifts and line mixing parameters, are all grouped together in the collisional relaxation matrix. To analyse the collisional process and physical effects on spectra of phosphine (PH₃), we have used the measurements carried out using a tunable diode-laser spectrometer in the ν₂ and ν₄ bands of PH₃ perturbed by hydrogen (H₂) at room temperature. The recorded spectra are fitted by the Voigt profile and the speed-dependent uncorrelated hard collision model of Rautian and Sobelman. These profiles are developed in the studies of isolated lines and are modified to account for the line mixing effects in the overlapping lines. The line widths, line shifts and line mixing parameters are given for six A₁ and A₂ doublet lines with quantum numbers K = 3n,?(n = 1,?2, …) and overlapped by collisional broadening at pressures of less than 50 mbar.     

Auger line shape analysis of Zn3P2

The technique of Auger line shape analysis is applied to Zn₃P₂ single crystal. Zn₃P₂ is a semiconductor that has some potential as a material suitable for solar energy conversion. The measured line shapes are band-like and so are amenable to analysis and comparison with theory. The line shapes are recovered from the spectra by background subtraction followed by the Van Cittert deconvolution. This technique is first applied to the L₃VV line of copper and the results checked against those already in the literature. The line shapes for Zn₃P₂ are compared with band structure calculations. In general, there is good agreement between the theory and our measured valence band structure.     

Line profile study from diode laser spectroscopy in the CH4 2ν3 band perturbed by N2, O2, Ar, and He

We present a line profile study for two lines in the 2ν₃ band of CH₄ recorded with a frequency stabilized tunable diode laser spectrometer. The broadening and narrowing (Dicke effect) parameters of the R(0) line perturbed by N₂, O₂, and He are derived from a simultaneous fitting of spectra at pressures from 20 to 300 Torr by using the soft and hard collision models. These parameters are determined for the A and F components of the unresolved R(3) manifold perturbed by N₂, Ar, and He from the line profile analysis of spectra at pressures between 50 and 500 Torr. The line mixing effect between the two F components is also taken into account and the absorber speed dependent effect on broadening is estimated for N₂ and Ar.     

Dissociative excitation due to collisions of electrons and helium ions with oxygen molecules

The absolute cross sections of luminescence related to atomic and ionic oxygen at dissociative excitation through e-O₂ and He⁺-O₂ collisions are determined. An intense OII line (83.4 nm) is discovered. For e-O₂ collisions, a weak OIII line (70.5 nm) is found. Experimental data for He⁺-O₂ collisions are qualitatively interpreted in terms of the quasi-diatomic approximation.     

Momentenanalyse derR 2-Nullphononen-Linie in NaF unter einaxialem Druck

The R₂ zero-phonon absorption line 4480 Å in NaF at 4.2 °K and 23 °K is studied under uniaxial stress along 〈100〉 and 〈100〉. According to the F₃ model of theR center the R₂ line is found to be due to a transition between a degenerate ground state (²E) and a nondegenerate excited state (²A) of this center. Instead of a splitting into single components under stress, changes in line shape are observed which are analyzed by means of the method of moments. The zeroth and first moment of the line are calculated as functions of the magnitude of stress and temperature. The theoretical moments are found to be in good agreement with those determined from the experimental data. From a comparison of the measured moments with the theoretical expressions the stress splitting parameters are obtained which describe the removal of both the orientational and the orbital degeneracy of theR center under uniaxial stress. The corresponding strain parameters of the R² line in NaF are compared with those in other alkali halides.     

The reverse shift of the EPR line of paramagnetic centers coupled to species with a fast paramagnetic relaxation

The EPR spectrum of the spin 1/2 paramagnetic centers with a relatively slow relaxation is considered in the case when they are coupled via the Heisenberg exchange interaction to partners which have short times of the longitudinal and transverse paramagnetic relaxation. Under these conditions only the EPR line of paramagnetic centers with a relatively slow relaxation is detectable in experiment. The shape of this line is analyzed by solving numerically kinetic equations for the spin density matrix for simple model systems. Depending on a ratio between the exchange integral and the paramagnetic relaxation rates of partner spins, the EPR line shifts in opposite directions. For moderate relaxation rates, as the relaxation rates decrease, the EPR line shifts toward the gravity center of the total EPR spectrum. In the case of extremely fast relaxation, as the relaxation rates decrease, the reverse shift of the EPR line is expected, the line shifts away from the gravity center of the total EPR spectrum. This type of the non-monotonous line shift was experimentally observed for the monocrystal of [CuNd₂(C₄O₄)₄(H₂O)₁₆] · 2H₂O when relaxation rates were changed by temperature variation.     

Measurement of N2O line strengths from high-resolution Fourier transform spectra

The absolute line strengths in four bands of nitrous oxide N₂O have been measured by means of the high information Fourier transform interferometer at the Laboratoire d'Infrarouge (apodized resolution: 5.4 × 10^?3 cm^?1). The investigated transitions were the 2ν₁ and ν₁ + 2ν₂ near 4 μm, and the ν₁ and 2ν₂ near 8 μm, which are all used for atmospheric detection. Conditions for extracting accurate line parameters are discussed. Reproducibility of measurements is better than 3% while absolute precision on both line and band intensities is shown to be currently better than 5%. Band intensity values compare well with the most recent determinations whereas the line strengths were never measured previously.     

CO2: Global Treatment of Vibrational–Rotational Spectra and First Observation of the 2ν1 + 5ν3 and ν1 + 2ν2 + 5ν3 Absorption Bands

The effective operator approach is applied to the calculation of both line positions and line intensities of the ¹³C¹⁶O₂ molecule. About 11 000 observed line positions of ¹³C¹⁶O₂ selected from the literature have been used to derive 84 parameters of a reduced effective Hamiltonian globally describing all known vibrational–rotational energy levels in the ground electronic state. The standard deviation of the fit is 0.0015 cm⁻¹. The eigenfunctions of this effective Hamiltonian have then been used in fittings of parameters of an effective dipole-moment operator to more than 600 observed line intensities of the cold and hot bands covering the ν₂ and 3ν₂ regions. The standard deviations of the fits are 3.2 and 12.0% for these regions, respectively. The quality of the fittings and the extrapolation properties of the fitted parameters are discussed. A comparison of calculated line parameters with those provided by the HITRAN database is given. Finally, the first observations of the 2ν₁ + 5ν₃ and ν₁ + 2ν₂ + 5ν₃ absorption bands by means of photoacoustic spectroscopy (PAS) is presented. The deviations of predicted line positions from observed ones is found to be less than 0.1 cm⁻¹, and most of them lie within the experimental accuracy (0.007 cm⁻¹) once the observed line positions are included in the global fit.     

Measured integrated band intensities and simulated line-by-line spectra for 12C2HD between 25 and 2.5 μm,and new global vibration–rotation parameters for the bending vibrations

The global analysis of published high-resolution vibration–rotation spectra of ¹²C₂HD in the bending spectral range is presented, resulting in an extension of the known vibration–rotation assignments, including a new band 2v₄+v₅←2v₄ (^IΠ←Δ). Experimental integrated band intensities are reported in the range from 25 to 2.5 μm, and both v₄ and v₅ bending fundamentals are simulated line by line. An extensive line list is produced in the bending energy range, to supply previously missing information in databases.     

Infrared multi-line NH3 laser and its application for pumping an InSb laser

In this paper, infrared (IR) emissions from a TE CO₂ laser pumped NH₃ laser are reported. 38 IR laser lines were obtained from a CO₂ 9R(30) line pumped NH₃ : N₂ mixture by cooling a NH₃ laser tube, and 13 lines of them were new emission lines as far as we known. Four Q-branch lines were included and the others belonged to P-branch transitions. The 12.078 μm line, which was the strongest line in this experiment, was used to pump an InSb spin-fip Raman (SFR) laser which could be tuned from 13.35 to 13.55 μm.     

Line shift and mixing in the ν4 and 2ν2 band of NH3 perturbed by H2 and Ar

Pressure induced line shift and line mixing parameters have been measured for 66 rovibrational lines in the ν₄ band and for 10 lines in the 2ν₂ band of NH₃ perturbed by H₂ and Ar at room temperature (T = 296 K). These lines with J values ranging from 2 to 10 are located in the spectral range 1450-1600 cm⁻¹. Experiments were made with a high-resolution Fourier transform spectrometer. The line shifts and line mixing parameters have been derived from the non-linear least-square multi-pressure fitting technique. The shift coefficients are compared with those calculated from the Robert-Bonamy formalism (RB). The results are generally in satisfactory agreement with the experimental data.     

Self-broadening, self-shift and self-mixing in the ν2, 2ν2 and ν4 bands of NH3

Using Fourier-transform spectra (Bruker IFS 120 HR, resolution ≈0.004 cm⁻¹) of NH₃ in nine branches of the ν₂, 2ν₂ and ν₄ bands, self-broadening and self-shift as well as self-mixing coefficients have been determined at room temperature (T=295 K) for more than 350 rovibrational lines located in the spectral range 1000–1800 cm⁻¹. A non-linear least-squares multispectrum fitting procedure, including line mixing effects, has been used to retrieve successively the line parameters from 11 experimental spectra recorded at different pressures of pure NH₃. The accuracies of self-broadening coefficients are estimated to be better than 2% for most lines. The mean accuracies of line-mixing and line-shift data are estimated to be about 15% and 25%, respectively. The results are compared with previous measurements and with values calculated using a semiclassical model based upon the Robert–Bonamy formalism that reproduces rather well the systematic experimental J and K quantum number dependencies of the self-broadening coefficients.The results concerning line mixing demonstrate a large amount of coupling between the symmetric and asymmetric components of inversion doublets mainly in the ν₄ band. The line mixing parameters are both positive and negative. More than two thirds of the lines studied here have a positive shift coefficient. However, for most of them the shift coefficients are negative in the 2ν₂ band. They are positive for the R branch of the ν₂ band and for the ^PR and ^RP branches of the ν₄ band. For the other branches they are both positive and negative. Some components of inversion doublets illustrate a correlation between line mixing and shift phenomena demonstrated by a quadratic pressure dependence of line position.     

High resolution polarization spectroscopy and laser induced fluorescence of CO<Subscript>2</Subscript> around 2μm

High resolution Infrared Polarisation Spectroscopy (IRPS) and Infrared Laser Induced Fluorescence (IRLIF) techniques were used to probe CO₂/N₂ binary gas mixture at atmospheric pressure and ambient temperature. The probed CO₂ molecules were prepared by laser excitation to an overtone and combination ro-vibrational state (12⁰1, J=15) of CO₂, centred at 4988.6612 cm^-1. IRPS and IRLIF line profiles were recorded for several CO₂/N₂ binary mixtures. The observed IRLIF line shapes have the expected Lorentzian form while the observed IRPS line shapes are narrower by a factor of two than those recorded with the IRLIF and appear to have a Lorentzian-cubed profile. The recorded line profiles provide measurements of the pressure-broadening coefficient directly at atmospheric pressure. The Full-Width-Half-Maxima (FWHM) pressure broadening coefficients are measured, based on IRLIF, to be 0.2174±0.0092 cm^-1atm^-1 and 0.1327 ±0.0077 cm^-1atm^-1 for self- and N₂ collision broadening, respectively. The broadening coefficients obtained based on IRPS were measured to be ~8% larger than those obtained with IRLIF.     

Raman line positions in molecular hydrogen: H2, HD,HT, D2, DT,and T2

Spontaneous Raman spectroscopy is used to determine line positions of the six isotopomers of molecular hydrogen: H₂, HD, HT, D₂, DT, and T₂. State populations as low as 1.3 × 10⁸ are detected with the present experimental apparatus. This sensitivity makes possible measurement of the first overtone Q-branch line positions for H₂ and D₂ and of higher rotational transitions than previous investigations. The line positions for D₂, DT, and T₂ indicate that literature values for molecular parameters do not predict accurately line positions of transitions at J values above the observed transitions from which they were determined. The results for the six molecular isotopomers show that ab initio energy levels restricted to the adiabatic approximation do not yield line positions within the experimental uncertainty whereas recent nonadiabatic calculations reproduce the present observations. Reexamination of literature results at high energies indicates discrepancies between the theoretical calculations and experimental vibrational band origins for all vibrational levels in HT, DT, and T₂. No experimental measurements are currently available that test the accuracy of nonadiabatic ab initio rotational levels at high energies.     

Analyses of the thermal shifts of spectral lines in Nd3+-doped LiYF4 laser crystal

The red-shift of spectral line E ₁(R ₁????Y ₂) and blue-shift of line E ₂(R ₁????X ₅) with temperature in Nd³⁺-doped LiYF₄ laser crystal are studied by considering both the static contribution due to lattice thermal expansion and vibrational contribution due to electron?Cphonon interaction. The study is based on the analyses of pressure and temperature dependences of these spectral lines. It is found that for both lines, the static and vibrational contributions result in the blue- and red-shift, respectively. So, the observed red-shift of line E ₁ and blue-shift of line E ₂ are due respectively to the static contribution being smaller and larger than the vibrational one. Also, we infer that the thermal shifts of lines E ₃(R ₁????Y ₅) and E ₄(R ₂????Y ₅) are very small because both contributions may be approximately canceled. When both the contributions are contained, whether the red-shift or blue-shift of a spectral line can be fitted with the almost same theoretical expression as that by including only the vibrational contribution used in red-shift in the previous papers if we change the expression concerning electron?Cphonon interaction coefficient.     

液芯光纤中溶液吸收和荧光的性质对CS2受激拉曼散射阈值的影响

利用液芯光纤技术研究了不同浓度的β-Carotene的CS₂溶液的吸收与荧光的特性对CS₂的一、二阶Stokes谱线阈值的影响.实验发现随溶液浓度(10^-8—10^-6 mol/L)增加，CS₂的一阶Stokes谱线的激发阈值相对变高；并且与纯CS₂芯液的受激拉曼散射相比较，在低抽运能量激发下，就观察到CS₂的二阶Stokes谱线.这主要是由于在CS₂的受激拉曼谱线产生的过程中，β-Carotene的CS₂溶液的吸收和荧光共同影响了CS₂的一、二阶Stokes谱线的阈值.我们进行了理论上的拟合与分析，其结果与实验符合很好. 关键词： 2受激拉曼散射阈值')" href="#">CS₂受激拉曼散射阈值 液芯光纤 吸收与荧光     

Raman scattering in Mg2Sn and Mg2Si

The Raman spectra of single crystal Mg₂Sn and Mg₂Si have been studied at room temperature. In Mg₂Sn we observe a single relatively strong line produced by the degenerate Raman active F_2g modes, seen previously by neutron inelastic scattering. Two weaker peaks are seen, one occuring at the F_2g overtone; the assignment for the other is uncertain. In Mg₂Si we find a strong line having a shift comparable to the value calculated by previous workers.     

The N2-broadened water vapor absorption line shape and infrared continuum absorption—II. Implementation of the line shape

The total line shape model of the previous paper is tested using a set of experimental room temperature H₂O continuum measurements of high quality. Parameters of the far wing component of the total line shape are determined from near band experimental data. Grating spectrometer measurements from 300 to 650 cm^?1 are used to determine unknown far wing parameters of the pure rotational band of H₂O. CO and HF laser measurements taken in the 5 and 3 μm regions are used to determine the far wing parameters of the ν₂ and ν₁, ν₃ fundamental bands, respectively.The total line shape model is applied to the 10 and 4 μm transmission windows with encouraging success. A significant increase in the self-broadening ability of H₂O over N₂ is predicted in the far wing. This procedure allows the proper modeling of the absorption coefficient vs H₂O partial pressure dependence in all window regions. A negative temperature is predicted by the model in the continuum. The observed rate of the temperature decrease is not predicted by the model; however, this limitation is related to the approximations made on the interaction potentials and the perturbation expansion of the Hamiltonians. Although the total line shape has limitations, it does demonstrate the importance of considering far wings of absorption lines in continuum absorption.     

Rotational CARS N2 thermometry: validation experiments for the influence of nitrogen spectral line broadening by hydrogen

Rotational coherent anti‐Stokes Raman spectroscopy (CARS) in fuel‐rich hydrocarbon flames, with a large content of hydrogen in the product gases (∼20%), has in previous work shown that evaluated temperatures are raised several tens of Kelvin by taking newly derived N₂ H₂ Raman line widths into account. To validate these results, in this work calibrated temperature measurements at around 300, 500 and 700 K were performed in a cell with binary gas mixtures of nitrogen and hydrogen. The temperature evaluation was made with respect to Raman line widths either from self‐broadened nitrogen only, N₂ N₂ [energy‐corrected‐sudden (ECS)], or by also taking nitrogen broadened by hydrogen, N₂ H₂ [Robert–Bonamy (RB)], Raman line widths into account. With increased amount of hydrogen in the cell at constant temperature, the evaluated CARS temperatures were clearly lowered with the use of Raman line widths from self‐broadened nitrogen only, and the case with inclusion of N₂ H₂ Raman line widths was more successful. The difference in evaluated temperatures between the two different sets increases approximately linearly, reaching 20 K (at T ∼ 300 K), 43 K (at T = 500 K) and 61 K (at T = 700 K) at the highest hydrogen concentration (90%). The results from this work further emphasize the importance of using adequate Raman line widths for accurate rotational CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman scattering in K2Pt(CN)4Br0.3 · 3H2O

Raman scattering experiments on K₂Pt(CN)₄Br_0.3 · 3H₂O are reported between 5 and 300 K as a function of temperature. A line of A₁ symmetry detected at 44 cm^?1 shows interesting temperature dependent properties. It is concluded from a comparison of the frequency, symmetry, and scattering intensity of this line with theoretical predictions that the excitation concerned represents the amplitude mode of the charge density wave (the line observed in infrared absorption being the phase mode). No Peierls transition is observed, but the results are consistent with a Peierls distortion present at all temperatures. The findings are correlated with inelastic neutron scattering and infrared studies. Finally, the CN stretching modes at 2189 and 2173 cm^?1 and the water mode at 3490 cm^?1 are studied as a function of temperature.