Comparison of band model and integrated line-by-line synthetic spectra for methane in the 2.3 μm region

The 2.3 μm spectral region of methane can be used to retrieve cloud properties of planetary spectra, provided parameters for the methane spectrum are known. Two standard techniques for calculating absorption spectra in this region are compared here. A Voigt profile Mayer-Goody random band model is applied, using coefficients empirically fitted by Fink et al. to CH₄ spectra recorded with high absorping amounts at 10 cm^?1 resolution. Calculation of the absorption is also done with a line-by-line direct integration method for the same gas conditions using molecular parameters obtained by combining an older unpublished list of observed positions and estimated line strengths (derived from 0.04 cm^?1 resolution data) with quantum assignments from the literature. The molecular parameters have been evaluated for the 4180–4590 cm^?1 region by comparing new laboratory spectra with 0.01 cm^?1 resolution recorded at 296 and 153K with synthetic spectra calculated at the same conditions. The deficiencies of the molecular parameters and random band coefficients for this spectral region of CH₄ are then discussed qualitatively and demonstrated by comparing 10 cm^?1 resolution synthetic spectra calculated by both methods for the same gas conditions at 296, 153, and 55 K.Curves of growth of the total equivalent width are calculated at 296 and 55K for a pathlength of 50 cm and pressures up to 10 atm. Changing the mean line spacing in the band model gives better agreement between the spectra calculated by the two techniques at low gas temperatures. The required multiplier has been determined for the mean line spacing for pressures from 10^?6 to 10^?1 atm at 55, 100, and 150 K.     

Absolute integrated intensity and individual line parameters for the 6·2μ band of NO2

The absolute integrated intensity of the 6·2μ band of NO₂ at 40°C was determined from quantitative spectra at ~ 10 cm^?1 resolution by the spectral band model technique. A value of 1430±300 cm^?2 atm^?1 was obtained. Individual line parameters, positions, intensities and ground state energies were derived, and line-by-line calculations were compared with the band model results and with the quantitative spectra obtained at ~ 0·5 cm^?1 resolution.     

Band model parameters for the 4.3 μm CO2 band from 200 to 3000°K—II. Prediction,comparison to experiment,and application to plume emission-absorption calculations

High resolution band-model parameters are presented for the 4.3 μm CO₂ band from 200 to 3000°K. Comparisons are made to experimental data covering this same temperature range. The band model predictions and data are shown to be in good agreement. Application of the band model parameters to plume emission and atmospheric absorption calculations in the CO₂ fundamental band head region (2380–2400 cm^-1) is discussed. Line-by-line and band-model plume signature predictions are compared for an aircraft and a rocket plume over 0, 0.5, and 5 km atmospheric paths. The line-by-line and band-model predictions for the 0 and 0.5 km paths are in good agreement. For the 5 km path, the band-model overestimates the atmospheric transmission by a factor of two. The reason for this overprediction is discussed and a correction is presented which improves the accuracy of the band-model transmission calculations.     

Remote sensing of high temperature H2O-CO2-CO mixture with a correlated k-distribution fictitious gas method and the single-mixture gas assumption

Infrared spectra of high temperature H₂O-CO₂-CO mixtures are calculated using narrow band models in order to simulate hot jet signature at long distance. The correlated k-distribution with fictitious gas (CKFG) approach generally gives accurate data in such situations (especially for long atmospheric paths) but results in long computation time in cases involving mixtures of gases. This time may be reduced if the mixture is treated as a single gas (single-mixture gas assumption, SMG). Thus the lines of the single-mixture gas are assigned to the fictitious gases. In this study, the accuracy of two narrow band models is evaluated. The first narrow band model considers one single-mixture gas and no fictitious gas (CK-SMG) whereas the second model accounts for one single-mixture gas and three fictitious gases (CKFG-SMG). Both narrow band models are compared with reference spectra calculated with a line-by-line (LBL) approach. As expected, the narrow band accuracy is improved by the fictitious gas (FG) assumption particularly when long atmospheric paths are involved. Concerning the SMG assumption, it may lead to an underestimation of about 10% depending on the variation of the gas mixture composition ratio. Nevertheless, in most of realistic situations the SMG assumption results in negligible errors and may be used for remote sensing of plume signature.     

Infrared radiation modeling of NO,OH, CO,H2O,and CO2 for emissivity/radiance prediction at high temperature

In the present study, infrared radiation modeling of NO, OH, CO, H₂O, and CO₂ molecules was devised based on a line-by-line method by utilizing a structured radiation analysis package, SPRADIAN07, coupled with up-to-date spectroscopic parameters and recent high-resolution radiation databases. An infrared calculation module was newly implemented in SPRADIAN07 for simulating the emissivity/radiance of NO and OH. The line positions of NO and OH molecules were determined by diagonalizing the Hamiltonian matrices of each molecule. The Einstein coefficients were obtained from either radiation databases or available calculated temperature-related line intensities. H₂O, CO₂, and CO were also modeled based on the high-resolution radiation databases, HITEMP2010 and CDSD-4000. When the line-by-line calculations were performed using the radiation databases, a parallel computing technique based on PC clusters was adopted for fast and efficient evaluation. The line-by-line model devised in the present study was validated by comparing the results with existing measurements. The simulations with room air absorption composed of H₂O and CO₂ were also carried out. The spectra taken from a plasma torch and those from a rocket plume were calculated by utilizing the present radiation model. It was shown that the calculated spectra are in good agreement with observed ones.     

Nitrogen-broadened lines of ethane at 150 K

Spectral transmittance has been measured in the v₉ fundamental band of C₂H₆ at 150 K using a Fourier transform spectrometer with apodized spectral resolution of 0.06 cm^-1. Comparison of observed spectral transmittance with a line-by-line computation using the spectral catalog of Atakan et al. has yielded N₂-broadened half-widths at 150 K.     

一种气体吸收的逐线计算模型及其实验验证

建立一种高分辨率的气体吸收光谱的逐线计算模型,分子谱线参数数据库采用了最新的低温库HITRAN2008和高温库HITEMP2010,能根据温度条件自动选择合适的谱带参数库,并可同时满足高温和常温气体辐射计算。计算波数采用等间隔取样,取样间隔大小以能分辨出典型分子谱线为条件确定。线翼截断采取等波数截断,总内配分函数由Gamache拟合三次多项式计算。谱线线型根据气体温度和压力来选择,最后,利用该模型计算了压力为1atm,不同温度、浓度和路径长度下CO2在4.3μm和2.7μm的透射率。考虑FTIR仪器增宽,将逐线计算结果降为窄带透射率,与中分辨率的试验结果对比均吻合,并能在较宽的温度范围内保证精度。     

红外扫描和频振动光谱系统的激光线宽与光谱分辨率

本文报道了一个简化的利用可见光和红外光带宽来计算和频光谱分辨率的公式. 公式显示和频振动光谱的Voigt线宽可以通过振动模式的均匀线宽(洛伦兹线宽)、非均匀线宽(高斯线宽)、红外光与可见光的高斯线宽计算获得. 利用本实验室新搭建的频率分辨及偏振分辨的皮秒和频光谱系统验证了该公式的准确性. 实验结果显示,本激光系统获取的红外光的高斯线宽为1.5 cm^-1. 本激光系统的光谱分辨率约为4.6 cm^-1,结果与胆固醇单层膜光谱获取的光谱分辨率(3.5~5 cm^-1)基本一致.     

Fast approximate technique for the cumulative wavenumber model to modeling radiative transfer in a mixture of real gas media

In the cumulative wavenumber (CW) model, the total range of the absorption cross-section Cη is subdivided into the supplementary absorption cross-section of gray gases C_j, j=1,…,n, where n is the number of gray gases; and the wavenumber region is subdivided into intervals Δ_i=[η_i−1, η_i], i=1, 2,…,p, where p is the number of intervals. The intersection of the two spectral subdivisions is used to define the modeling of the fractional gray gas D_ij. In the CW model, we solve the radiative transfer equation (RTE) in every subinterval D_ij; then it is necessary to solve n x p times the spectral form of the RTE for complete spectral integration. In this work, the CW model is used with a numerical approximation technique based on additive properties of radiative intensity to reduce the solution of RTE to n new fractional gray gas D_j for complete spectral integration. The CW model was first coupled with the discrete ordinates method and the accuracy of the simplified technique and the algorithm was first examined for one-dimensional homogeneous media; results are compared with line-by-line calculations and it is found that the CW model with the simplified technique is exact for the homogeneous media examined. Also, the fast approach is tested in the diffuse reflecting boundaries case. The CW model is implemented in a bi-dimensional enclosure containing real gases in isothermal cases. Afterwards, this approximate technique is extended to non-isothermal and non-homogeneous cases; the results are compared with line-by-line calculations taken from literature and good agreement was found. The results obtained using the acceleration technique for the CW model agree with the results of original CW model. With this acceleration technique the CPU time decreases p times. Spectral database HITRAN and HITEMP are used to obtain the molecular absorption spectrum of the gases.     

The ν2 + ν4 and 2ν2 isotropic Raman bands of 12CH4

The purely isotropic Raman spectrum of the ν₁ band, the ν₂ + ν₄ band (enhanced through interaction with ν₁), and the 2ν₂ band of ¹²CH₄ was obtained with a spectral resolution of 0.30–0.35 cm^?1 from exposures with different orientations of the linearly polarized exciting light. The ν₂ + ν₄ and 2ν₂ bands show partially resolved rotational structure. The spectra are interpreted in terms of a model which takes explicitly into account vibrational and rovibrational interactions with other vibrational states, using molecular constants determined primarily from infrared spectra. The computed contours are in excellent agreement with the experimental ones and the observed and calculated peak wavenumbers agree within one tenth of the spectral resolution limit, except for a small region near the ν₁ band. The good overall agreement represents an independent check on the overall correctness of the previously reported molecular constants. A detailed discussion is given of the contributions to the intensities of individual transitions from the three transition moment matrix elements, which in an isolated-band model are the intensity parameters of the ν₁, 2ν₄, and 2ν₂ isotropic bands, respectively.     

High resolution infrared spectrum of the CD2 wagging band of methanol-D2 (CHD2OH) for the lowest lying torsional vibrational state (e0)

This paper reports the analysis of the high resolution (0.0019 cm⁻¹) Fourier transform infrared (FTIR) spectrum for asymmetrically deuterated methanol CHD₂OH (methanol-D₂) at a low temperature for the CD₂ wagging band for the lowest lying trans-species (e₀). In spite of the complexity and perturbation in the spectra, assignments were possible for the CD₂ wagging band for a maximum K value of 10. In total, about 500 spectral lines have been assigned. Analysis of the spectral lines has been performed in terms of state dependent molecular parameters, Q-branch origins and asymmetry splitting. Assignments have been thoroughly confirmed using combination relations (see text). The catalogue of the assigned transition wavenumbers will help identification and prediction of far infrared (FIR) optically pumped CO₂ lasers. The absorption lines close to the several 10R and 10P CO₂ laser lines have also been identified. These should help experimentalists to optimize the power of the emission FIR laser lines and to predict new lines and should prove valuable as a laboratory support for interstellar detection in “Radio Astronomy”. To our knowledge this is the first time such vibrational infrared (IR) high resolution study in CHD₂OH is being performed.     

The spectral-line moment-based (SLMB) modeling of the wide band and global blackbody-weighted transmission function and cumulative distribution function of the absorption coefficient in uniform gaseous media

The spectral-line moment-based (SLMB) modeling is proposed for the calculation of radiative properties of gases on any spectral width. The associated mathematical formulation is obtained by applying several concepts of the k-distribution methods such as the reordering of the wavenumber scale by monotonic variations of the absorption coefficient, together with the application of the k-moment method's principles. This approach gives both a general formula for the BTF and a simple and readily applicable approximation for the blackbody-weighted cumulated k-distribution function of the absorption coefficient. The model is applied for the computation of wide band BTFs and cumulative k-distributions for uniform columns of CO₂ and H₂O in the temperature range (300-2400 K) at atmospheric pressure. Model parameters are deduced from line-by-line (LBL) spectra calculated using the HITEMP database. Comparisons with LBL reference data as well as with contemporary modeling approaches (SLW, FSK, SNB) are performed and discussed.     

Infrared radiation characteristics of liquid oxygen/kerosene rocket engine plume with different number of nozzles

A method for calculating the liquid oxygen (LOX)/kerosene rocket engine plume infrared radiation characteristics was proposed, infrared radiation characteristics of the gas oxygen/kerosene model engine were studied by simulation and experiment, and the accuracy of the method was proved. On this basis, studies on infrared spectral radiation characteristics and infrared imaging characteristics of single- and double-nozzle 120?ton thrust LOX/kerosene engine plume were carried out. It is found that, the engine nozzle number can be determined according to infrared imaging characteristics of the engine plume at the appropriate detection angle. Compared to using 2–5?µm band, the infrared radiation imager with clearer plume structure can be obtained using the spectral band such as 2.7 and 4.3?µm bands. The change in the detection angle and the increase in the engine number will have a significant effect on the infrared radiation intensity of the LOX/kerosene engine plume, but they will not change the infrared spectral radiation characteristics.     

The method of lines solution of discrete ordinates method for non-grey media

A radiation code based on method of lines (MOL) solution of discrete ordinates method (DOM) for radiative heat transfer in non-grey absorbing-emitting media was developed by incorporation of a gas spectral radiative property model, namely wide band correlated-k (WBCK) model, which is compatible with MOL solution of DOM. Predictive accuracy of the code was evaluated by applying it to 1-D parallel plate and 2-D axisymmetric cylindrical enclosure problems containing absorbing-emitting medium and benchmarking its predictions against line-by-line solutions available in the literature. Comparisons reveal that MOL solution of DOM with WBCK model produces accurate results for radiative heat fluxes and source terms and can be used with confidence in conjunction with computational fluid dynamics codes based on the same approach.     

A computer study of the absorption spectra of the water-carbon monoxide disperse system

The IR absorption, emission, and reflectance spectra of (CO) _i (H₂O)₂₀, 1 ≤ i ≤ 10, clusters were calculated using the molecular dynamics model. After the adsorption of CO molecules by clusters, IR radiation absorption and reflection by the system composed of them weakened, whereas thermal radiation power increased. We tracked changes in spectral characteristics as the number of molecules in clusters increased. Growing water clusters decreased absorption and gradually increased IR emission power. The growth of a water cluster with the addition of CO molecules to it as a rule caused the opposite effect. On the whole, clusterization and the entrapment of CO molecules by clusters had an antigreenhouse effect.     

Narrow resonances (Δv=2·10−2 cm−1) of multiple-photon IR absorption in ethylene

Narrow peaks of multiple-photon absorption in thev ₇ band of ethylene with the spectral width 0.02 cm⁻¹ and the contrast factor of up to 10² have been observed at the intensity of laser radiation 0.04 and 0.6 MW/cm². The multiple-photon spectra of ethylene in intense IR field have been studied with the use of a quasi-single-mode continuously tunable CO₂ laser. The results of the experiments are interpreted within the model of spepwise molecular excitation due to weak transitions.     

Infrared absorption by gas mixtures in the 500—700 K temperature range II— 2.7 μm H2O spectra

The absorption spectra of water vapor in the 2.7 μm-band have been obtaine in an isothermal, vacuum-tight cell with a resolution of 0.8 cm^-1. They are compared with a line-by-line calculation using AFGL data and the approximate temperature-dependence of the line-widths. Agreement is very satisfactory in some spectral regions and rather poor in others.     

Diagnostics of laser-produced plume under carbon nanotube growth conditions

This paper presents diagnostic data obtained from the plume of a graphite composite target during carbon nanotube production by the double-pulse laser oven method. The in situ emission spectrum (300 to 650 nm) is recorded at different locations upstream of the target and at different delay times from the lasers (IR and green). Spectral features are identified as emissions from C₂ (Swan System: d³@_g-a³@_u) and C₃ (Comet Head System: A¹@_u-X¹D_u⁺). Experimental spectra are compared with computed spectra to estimate vibrational temperatures of excited state C₂ in the range of 2500 to 4000 K. The temporal evolution of the 510-nm band of C₂ is monitored for two target positions in various locations, which shows confinement of the plume in the inner tube and increase in plume velocity with temperature. The excitation spectra of C₂ are obtained by using a dye laser to pump the (0,1) transition of the Swan System and collecting the laser-induced fluorescence signal from C₂. These are used to obtain "ground-state" rotational and vibrational temperatures which are close to the oven temperature. Images of the plume are also collected and are compared with the spectral measurements.