CARS methane spectra: Experiments and simulations for temperature diagnostic purposes

CARS laboratory experiments were done in the 2905–2925 cm⁻¹ range, in the vicinity of the ν₁ band of the methane molecule, for pressures ranging from 1 to 50 bar, and temperatures up to 1100 K. These experiments were carried out in order to retrieve the pressure evolution of the CH₄ spectrum, as well as to confirm its temperature dependance. After a brief recall on the theory used to compute pressure broadening coefficients and relaxation rates, we consider the ν₃ and ν₄ infrared bands of methane for benchmark calculations purposes. Next, we present recent experimental CARS spectra and calculated ones. Lastly, we discuss flame experiments as well as comparisons of temperature retrieval using N₂ and CH₄ as probe molecules.     

Isotopic substitution shifts in methane and vibrational band assignment in the 5560-6200 cm region

The absorption spectra of the ¹²CH₄ and ¹³CH₄ molecules have been recorded and assigned in the 5560-6200 cm⁻¹ region. The effects of isotopic substitution for ¹²C by ¹³C on the methane vibrational energy levels have been calculated from an ab initio potential energy surface and compared with experiment. Comparison of the results obtained for two isotopic species allows us to confirm the vibrational assignment for the strongest bands of ¹²CH₄ in this region. Good agreement of ab initio calculations with observed energy levels has been demonstrated. A list of the assigned ¹³CH₄ lines valuable in atmospheric applications is reported.     

The 1.58 μm transparency window of methane (6165-6750 cm): Empirical line list and temperature dependence between 80 and 296 K

The empirical line parameters of over 12,000 methane transitions have been obtained at 80 K in the 1.58 μm transparency window (6165-6750 cm⁻¹) which is of importance for planetary applications. This line list (WKC-80K) was constructed from high sensitivity spectra of normal abundance methane recorded by CW-Cavity Ring Down Spectroscopy at low temperature. The minimum intensity reported is on the order of 5×10⁻³⁰ cm/molecule. High resolution Fourier transform spectra have also been recorded using enriched CH₃D samples at 90-120 K in order to facilitate identification of monodeuterated methane features in the methane line list at 80 K. The CH₃D relative contribution in the considered region is observed to be much larger at 80 K than at room temperature. In particular, CH₃D is found dominant in a narrow spectral window near 6300 cm⁻¹ corresponding to the highest transparency region.Using a similar line list constructed at room temperature (Campargue A, Wang L, Liu AW, Hu SM and Kassi S. Empirical line parameters of methane in the 1.63-1.48 μm transparency window by high sensitivity Cavity Ring Down Spectroscopy. Chem Phys 2010;373:203-10.), the low energy values of the transitions observed both at 80 K and at room temperature were derived from the variation of their line intensities. Empirical lower states and J-values have been obtained for 5671 CH₄ and 1572 CH₃D transitions representing the most part of the absorbance in the region. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH₄ lower state J values to be close to integers. The WKC line lists at 80 K and room temperature provided as Supplementary Material allow one accounting for the temperature dependence of methane absorption between these two temperatures. The importance of the 80 K line list for the study of Titan and other methane containing planetary atmospheres is underlined and further improvements are proposed. The resulting information will advance the theoretical modeling of the methane spectrum in the 1.58 μm transparency window.     

自受激拉曼晶体Nd3+:SrMoO4的光谱性质研究

通过拉曼散射光谱，吸收光谱，荧光发射寿命和808 nm LD激发下的红外荧光光谱的实验测量，系统研究了Nd³⁺:SrMoO₄晶体的自受激拉曼光谱性质.分析指认了拉曼散射光谱中各拉曼峰所对应的晶格振动模式，得出了其SRS活性最强的声子频率约为898 cm^-1，对应于(MoO^2-₄)离子团的完全对称光学伸缩振动A_g模；通过J-O理论对晶体的吸收谱进行了全面的光谱参数计算，得出⁴F_3/2→⁴I_11/2跃迁的积分发射截面达0.57×10^-18 cm²，自发辐射概率为141.06 s^-1；同时，实验测得该跃迁的荧光发射寿命约为0.2 ms.最后，结合808 nm LD激发下的红外波段荧光光谱，论证了SrMoO₄晶体中Nd³⁺离子1068 nm发射通过拉曼频移获得1180 nm一级斯托克斯激光发射的可能性，为Nd³⁺:SrMoO₄晶体的自受激拉曼激光器研究提供了理论依据. 关键词： 3+离子')" href="#">d³⁺离子 4 晶体')" href="#">SrMoO₄ 晶体 自受激拉曼散射     

Determination of the low energy values of CH4 transitions in the 2ν3 region near 1.66 μm from absorption spectra at 296 and 81 K

The high resolution absorption spectra of ¹³CH₄ were recorded at 81 K by differential absorption spectroscopy using a cryogenic cell and a series of distributed feed back (DFB) diode lasers and at room temperature by Fourier transform spectroscopy. The investigated spectral region corresponds to the high energy part of the ¹³CH₄ tetradecad dominated by the 2ν₃ overtone near 5988 cm⁻¹. Empirical line lists were constructed containing, respectively, 1629 ¹³CH₄ transitions detected at 81 K (5852-6124 cm⁻¹) and 3481 features (including 85 lines of ¹²CH₄) measured at room temperature (5850-6150 cm⁻¹); the smallest measured intensities are about 3 × 10⁻²⁶ and 4 × 10⁻²⁵ cm/molecule at 81 and 296 K, respectively. The lower state energy values were derived for 1196 ¹³CH₄ transitions from the variation of the line intensities between 81 and 296 K. These transitions represent 99.2% and 84.6% of the total absorbance in the region, at 81 and 296 K, respectively. Over 400 additional weak features were measured at 81 K and could not be matched to lines observed at room temperature. The quality of the resulting empirical low energy values is demonstrated by the excellent agreement with the already-assigned transitions and the clear propensity of the empirical low J values to be close to integers. The two line lists at 81 and at 296 K provided as Supplementary material will enable future theoretical analyses of the upper ¹³CH₄ tetradecad.     

High sensitivity absorption spectroscopy of methane at 80 K in the 1.58 μm transparency window: Temperature dependence and importance of the CH3D contribution

The high resolution absorption spectrum of methane in the 1.58 μm transparency window has been recorded at room temperature and at 79 K by CW-Cavity Ring Down Spectroscopy using a cryogenic cell and a series of Distributed Feed Back (DFB) diode lasers. The achieved sensitivity (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹) has allowed for a detailed characterization of the 6289-6526 cm⁻¹ region which corresponds to the lowest opacity of the transparency window. A list of 6868 and 4555 transitions with intensities as weak as 1 × 10⁻²⁹ cm/molecule was constructed from the recordings at 297 and 79 K, respectively. By comparison with a spectrum of CH₃D recorded separately by Fourier Transform Spectroscopy, 1282 and 640 transitions of monodeuterated methane, CH₃D, in natural abundance in our sample were identified at 297 and 79 K, respectively.The rotational temperature determined from the intensity distribution of the 3ν₂ band of CH₃D (79.3 K) was found in good agreement with the temperature value previously obtained from the Doppler line broadening. The reduction of the rotational congestion by cooling down to 79 K reveals a spectral region near 6300 cm⁻¹ where CH₃D transitions are dominant.The low energy values of the transitions observed both at 79 K and at room temperature were derived from the variation of their line intensities. These transitions with lower energy determination represent 93.9% and 68.4% of the total absorbance in the region, at 79 K and room temperature, respectively. The quality of the obtained empirical low energy values is demonstrated for CH₄ by the marked propensity of the empirical low J values to be close to integers. The line lists at 79 K and room temperature provided as Supplementary Material allow accounting for the temperature dependence of methane absorption between these two temperatures. The investigated region covering the 5ν₄ band of the ¹²CH₄ isotopologue will be valuable for the theoretical treatment of this band which is the lowest energy band of the icosad.     

Laser Raman study of phase transformations in [N(CH3)4]2ZnCI4 single crystals

We report temperature-dependent Raman studies on single crystals of [N(CH₃)₄]₂ZnCI₄ from 300 to 10 K. The observed spectral features suggest that both the N(CH₃)₄ ⁺ and ZnCl^2- ₄ ions are distorted from their regular tetrahedral structure and occupy sites of C_s symmetry in the lattice at room temperature. From the variation of line width of some selected Raman bands and other spectral changes as a function of temperature, it is inferred that both the ZnCl^2- ₄ and—CH₃ groups have high motional freedom at room temperature and the different phase transitions up to 160 K are triggered by the gradual freezing-in of orientational freedom of these groups, while the N—C₄ tetrahedra do not play any significant role in these phase transitions. The monoclinic to orthorhombic superlattice phase transitions at 159 K is triggered by freezing-in of the orientational motions of both the ZnCl^2- ₄ and N(CH₃)⁺ ₄ groups in the lattice.     

Optical observation of ion displacement in pyroelectric BaMnF4

Two anomalous behaviors are observed in the Raman spectra of BaMnF₄ at room temperature. One is that the number of Raman lines is smaller than that expected for the orthorhombic crystal structure with C _2ν ¹² symmetry, the other is that, of the b(aa)c, a(bb)c, and b(cc)a scattering geometries giving the same A₁-symmetry spectrum, the number of Raman lines in the b(aa)c spectrum is considerably smaller than those in the other two spectra. It is suggested that rotation of MnF₆ octahedra about c-axis occurring in the orthorhombic phase is responsible for the former behavior, and Ba²⁺-ion displacement along a-axis for the latter one.     

Laser spectroscopic monitoring of gas emission and measurements of the C/C isotope ratio in CO2 from a wood-based combustion

We report on the application of a compact and field-deployable instrument, based on a continuous-wave fiber-coupled Telecom external cavity diode laser, to measure the ¹³C/¹²C isotope ratio in CO₂ from a wood-based combustion. Carbon dioxide, the most important greenhouse gas, is a major product of combustion. The measurements of the ¹³C/¹²C isotopic ratio in CO₂ from combustion emission permit one to identify the CO₂ source and to study the temporal and spatial variations of pollution in the atmosphere. The average value of the ¹³CO₂/¹²CO₂ ratio is found to be (1.1011±0.0024)%. The corresponding δ-value relative to PDB standard is (−20.17±2.14)‰, which is in good agreement with the typical value of (−25±2)‰ for wood. Simultaneous monitoring of multiple species from gas emission has been performed using direct-absorption spectroscopy. The concentrations of C₂H₂, CO, CO₂ and H₂O were determined on the basis of integrated absorbance measured by least-squares fitting a Voigt lineshape to experimental absorption spectra.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

The CH3D absorption spectrum in the 1.58 μm transparency window of methane: Empirical line lists at 81 K and 294 K and temperature dependence

In spite of its low isotopic abundance in methane (about 5×10⁻⁴), CH₃D contributes greatly to the very weak absorption in the 1.58 μm methane transparency window. This methane window deserves to be characterized in details because it is important for planetary applications in particular for Titan and the giant planets. In this work, we recorded the CH₃D spectrum by high sensitivity differential absorption spectroscopy (α_min≈5×10⁻⁸ cm⁻¹) both at room temperature and at 81 K. A list of more than 9000 lines was constructed from the 81 K spectrum for the 6099–6530 cm⁻¹ region. In order to get the temperature dependence of the line intensities, the low energy values have to be determined. The rovibrational assignments available in the literature provide low energy values for about 380 strong transitions of the region. This is insufficient to characterize the temperature dependence of the CH₃D absorption between 6200 and 6400 cm⁻¹. In this interval, a list of 5500 lines was constructed from the room temperature spectrum. The empirical energy values of the transitions were derived from the ratio of the intensities at 81 K and 294 K. The exact and empirical lower state energies included in the final line lists provided as Supplementary Material, allow for accounting for the temperature dependence of the CH₃D spectrum in the entire 6099–6530 cm⁻¹ region.Our measurements have been compared to the spectroscopic parameters and assignments available in the literature in particular those adopted in the HITRAN database. Improvements and corrections are proposed for the wavenumber calibration and for some lower state energies.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

Reinvestigation of the ν2 + 2ν3 subband in the overtone icosad of 12CH4 using cavity ring-down (CRD) spectroscopy of a supersonic jet expansion

We report a detailed reinvestigation of the ν₂?+?2ν₃ combination band of methane ¹²CH₄ centred at (7510.3378?±?0.003)?cm^?1 ((225.154263?±?0.0001)?THz) within the icosad of the overtone absorption. A new experimental setup is described, allowing us to carry out cw-laser cavity ring-down spectroscopy (cw-CRDS) at instrumental resolution in the MHz range in seeded supersonic jet expansions down to rotational temperature of 7?K compared to previous cw-CRDS measurements in our group achieving about 50?K in expansions of neat CH₄. We provide a careful re-analysis on the basis of our new experimental results for the Q and R branch transitions including data obtained between about 7 and 300?K under various conditions. We resolve previously observed discrepancies of assignments and are able to present a definitive assignment for lines involving angular momentum quantum numbers up to J?=?4. The analysis of relative intensities in spectra taken at rotational and effective translational temperatures between about 50?K and less than 10?K indicate conservation of nuclear spin symmetry upon supersonic jet expansion, in agreement with previous results using other techniques and covering other spectral ranges.     

Raman,Infrared and 1H-NMR Spectra of Hexamethyldisilylchalcogenides

The Raman, infrared and ¹H-NMR spectra of (CH₃)₃ -X-Si (CH₃)₃ (X=O,S,Se,Te) were measured, and the assignment was carried out by comparison with those of the structurally related compounds, (CH₃)₃ SiCl and (CH₃)₃ Si-Si (CH₃)₃. The vibrational spectra of (CH₃)₃ Si-X-Si (CH₃)₃ can be interpreted in terms of a non-rigid D_3d symmetry with internal rotations, because those of skeletones of the molecules indicate the lack of coincidence between Raman and infrared frequencies. The ¹H-NMR spectra also support a non-rigid D_3d model, because only one band for CH₃ group appears.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

Preparation and luminescence properties of Tb doped ZrO2 and BaZrO3 phosphors

ZrO₂:Tb³⁺ and BaZrO₃:Tb³⁺ powders are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 1000 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction, Raman spectra and scanning electron microscopy. It is remarkable that all the samples of ZrO₂:Tb³⁺ and BaZrO₃:Tb³⁺ have similar morphology. These images exhibited homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small cuboids and broken cuboids. The cuboids and broken cuboids size of all the samples are less than 0.5 μm. Photoluminescence for both materials increases with increase of temperature and found maximum for the samples heated to 1000 °C with 5 mole% doping of Tb³⁺ ions. Luminescence is almost double for the zirconia compared to that of barium-zirconate.     

Partial and complete methane oxidation in supercritical water

The paper represents results on investigation of methane oxidation in supercritical water (SCW) in autoclave and flow conditions. In the autoclave, oxidation is realized under uniform heating of a CH₄/O₂/H₂O and CH₄/O₂/N₂ mixture to 873 K (the water and nitrogen density ≈ 3.2 mmol/cm³, the molar ratio [O₂]₀/[CH₄]₀ ≈ 1 and 2). In the composition of the oxidation products we detected H₂ (only at [O₂]₀/[CH₄]₀ ≈ 1), CO and CO₂. Based on time dependences of the reaction mixture temperature we have found that temperature of the onset of self-heating of the CH₄/O₂/H₂O mixture is lower by 23 K than that of the CH₄/O₂/N₂ mixture and grows as the CH₄ concentration decreases. For comparable values of self-heating the average power in CH₄ combustion in the H₂O medium has appeared to be about two orders lower than in the N₂ medium, which evidences inhibition of SCWmethane oxidation. In the boiler-reactor, oxidation was realized while mixing CH₄ and O₂ in counter-propagating jets in the cocurrent upflow of SCW at 673–874 K, 30 MPa (molar ratio [O₂]/[CH₄] ≈ 2.2). Unsteady combustion was observed only at a reaction mixture temperature of 678 K, which became steady at 700 K after a series of flashes. The carbon-bearing methane oxidation products in the boiler-reactor contain only CO₂ (≥ 97.5%) and CO (≤ 2.5%mole).     

Homogeneous ignition of CH4/air and H2O and CO2-diluted CH4/O2 mixtures over Pt; an experimental and numerical investigation at pressures up to 16 bar

The homogeneous ignition of CH₄/air, CH₄/O₂/H₂O/N₂, and CH₄/O₂/CO₂/N₂ mixtures over platinum was investigated experimentally and numerically at pressures 4 bar p 16 bar, temperatures 1120 K T 1420 K, and fuel-to-oxygen equivalence ratios 0.30 0.40. Experiments have been performed in an optically accessible catalytic channel-flow reactor and included planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous (gas-phase) ignition and one-dimensional Raman measurements of major species concentrations across the reactor boundary layer for the assessment of the heterogeneous (catalytic) processes preceding homogeneous ignition. Numerical predictions were carried out with a 2D elliptic CFD code that included elementary heterogeneous and homogeneous chemical reaction schemes and detailed transport. The employed heterogeneous reaction scheme accurately captured the catalytic methane conversion upstream of the gaseous combustion zone. Two well-known gas-phase reaction mechanisms were tested for their capacity to reproduce measured homogeneous ignition characteristics. There were substantial differences in the performance of the two schemes, which were ascribed to their ability to correctly capture the p–T– parameter range of the self-inhibited ignition behavior of methane. Comparisons between measured and predicted homogeneous ignition distances have led to the validation of a gaseous reaction scheme at 6 bar p 16 bar, a pressure range of particular interest to gas-turbine catalytically stabilized combustion (CST) applications. The presence of heterogeneously produced water chemically promoted the onset of homogeneous ignition. Experiments and predictions with CH₄/O₂/H₂O/N₂ mixtures containing 57% per volume H₂O have shown that the validated gaseous scheme was able to capture the chemical impact of water in the induction zone. Experiments with CO₂ addition (30% per volume) were in good agreement with the numerical simulations and have indicated that CO₂ had only a minor chemical impact on homogeneous ignition.     

12CH2F2 and13CH2F2far-infrared lasers: New lines and frequency measurements

We report here the discovery of 13 new far-infrared laser lines from¹²CH₂F₂ and seven new lines from¹³CH₂F₂. Most of the new lines were pumped by high-J lines of the 9R branch of a cw-CO₂ laser. Wavelengths range from 97.6 to 616.18 μm. Frequency, pump offset, relative polarization, and relative intensity were measured for most of the new lines.     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.