Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz

The air induced broadening coefficients of the pure rotational transitions of H₂O at 556.936 GHz (1₁₀←1₀₁), and 752.033 GHz (2₁₁←2₀₂) were measured by terahertz time-domain spectroscopy. The air broadening coefficient was determined to be for the 556.936 GHz line and for the 752.033 GHz line, respectively. The present broadening coefficients for the 556.936 GHz water line are significantly smaller than those of Markov and Krupnov [Measurements of the pressure shift of the 1(10)-1(01) water line at 556.936 GHz produced by mixtures of gases. J Mol Spect 1995:172;211-4] but relatively close to the values of the HITRAN database. The measured data may improve the accuracy of the abundance of water vapor retrieved from spectra obtained by the Odin/SMR satellite instrument. The effect on the satellite retrieval processing is discussed.     

Pressure shift and broadening of 110-101 water vapor lines by atmosphere gases

This paper is devoted to the measurement of pressure shift and broadening parameters of water-vapor lines of the pure rotational transition 1₁₀-1₀₁ in the ground vibrational state of H₂¹⁶O at 556.936 GHz, H₂¹⁷O at 552.02 GHz, H₂¹⁸O at 547.676 GHz, and the vibrationally excited state v₂=1 line of H₂¹⁶O at 658.003 GHz. The broadening coefficients of the line at 556.936 GHz (for N₂ and O₂ as perturbing gases) coincide within the errors with the values obtained recently by Seta et al. [Pressure broadening coefficients of the water vapor lines at 556.936 and 752.033 GHz. JQSRT 2008;109:144-50] by means of a very different technique (THz-TDS). Pressure shift and broadening for other lines were measured for the first time. Comparison of our results with previous measurements and theoretical calculations is presented.     

Collisional broadening and shifting of the 211-202 transition of H2O, H2O, H2O by atmosphere gases

Broadening and shifting of the 2₁₁-2₀₂ transition of H₂¹⁶O, H₂¹⁷O, H₂¹⁸O by pressure of water, nitrogen and oxygen were precisely measured at room temperature using spectrometer with radio-acoustic detection of absorption. Shift parameters for all studied lines as well as broadening parameters of H₂¹⁷O, H₂¹⁸O lines were measured for the first time. Comparison of obtained results with previously known experimental and theoretical data is presented.     

Comparison between theoretical calculations and high-resolution measurements of pressure broadening for near-infrared water spectra

We report N₂ and air foreign pressure broadening coefficients of more than twenty rovibrational transitions of water vapor in the 935-nm spectral region, and these measurements are compared to new theoretical calculations. The data were obtained using the frequency-stabilized cavity ring-down spectroscopy method, yielding relative uncertainties for the broadening parameters in the range 0.4-2.2%. The sensitivity of measured broadening parameters to the choice of line shape functions is discussed, and systematic differences between experimentally determined collisional broadening coefficients are shown for the cases when the observed line narrowing is interpreted in terms of Dicke-narrowing or the speed-dependence of the collisional broadening and shifting. Theoretical models of pressure broadening for these transitions agree with the measurements to within 4% for most transitions with an average relative difference of 0.63%.     

Adjoint problem of radiative transfer for a pseudo-spherical atmosphere and general viewing geometries

We formulate the adjoint radiative transfer for a pseudo-spherical atmosphere and various retrieval scenarios. The single scattering radiance is computed in a spherical atmosphere by using the source integration technique, while for the multiple scattering radiance we formulate an one-dimensional adjoint radiative transfer equation in a plane-parallel atmosphere. The adjoint solution of the radiative transfer equation is obtained by employing the discrete ordinate method with matrix exponential. We provide an abbreviated derivation of our formalism as well as a discussion of the numerical implementation of the theory.     

水汽多线光声光谱中压力线位移及加宽系数的分析

本工作从水汽的多线光声光谱中分析得到压力线位移和加宽系数。为了提高系数的精度和拟合效率，采用了Ｖｏｉｇｔ线型和参数分组约束优化方法。     

Pressure broadening and shifting parameters for the spectral lines in the fundamental vibration-rotation bands of HBr and HI in mixtures with rare gases

We report measurements of the line broadening and shifting coefficients in the (1 ← 0) fundamental absorption bands of the HBr and HI molecules in mixtures with rare gases He, Ne, Ar, Kr, and Xe. Comparison is given with the published data on other HHal-Rg systems. The measured line shifts are separated into terms symmetric and asymmetric in the line number m. The magnitudes of the symmetric shifts change in a regular manner in the series of rare gases and reach perturber-specific asymptotic values at higher ∣m∣. It is found that the asymptotic values of the symmetric line shifts linearly correlate with the respective C₆ potential energy constants and that the slopes of these correlations are proportional to the vibrational ground state dipole moments squared of the hydrogen halide molecules.     

Pressure broadening and shifting parameters for the spectral lines in the first overtone vibration-rotation bands of HBr and HI in mixtures with rare gases

We present experimental data on the previously unknown line broadening and shifting coefficients in the (2 ← 0) overtone vibration-rotation bands of the HBr and HI molecules in mixtures with several rare gases. The vibrational dependence of the isotropic and anisotropic components of the binary interaction potential is probed by separating the measured line shifts into parts symmetric and asymmetric in the line number m and by comparing with the previously published similar data for the fundamental bands of the same molecules. It is shown that the line shifts are dominated by the vibrational dependence of the isotropic potential. A linear correlation is found between the asymptotic values of the symmetric shifts in the overtone bands for all HX-Rg (X = F, Cl, Br, I) pairs and the respective C₆ long-range potential energy constants. Line broadening parameters in the overtone band of pure HBr are also reported.     

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.     

Pressure broadening and collisional shift of the Rb D2 absorption line by CH4, C2H6, C3H8, n-C4H10, and He

The pressure broadening and shift rates of the rubidium D2 absorption line 5²S_1/2→5²P_3/2 (780.24 nm) with CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He were measured for pressures ≤80 Torr using high-resolution laser spectroscopy. The broadening rates γ_B for CH₄, C₂H₆, C₃H₈, n-C₄H₁₀, and He are 28.0, 28.1, 30.5, 31.3, and 20.3 (MHz/Torr), respectively. The corresponding shift rates γ_S are −8.4, −8.8, −9.7, −10.0, and 0.39 (MHz/Torr), respectively. The measured rates of Rb for the hydrocarbon buffer gas series of this study are also compared to the theoretically calculated rates of a purely attractive van der Waals difference potential. Good agreement is found to exist between measured and theoretical rates.     

Pressure broadened calculations of the OCSJ = 1 → 2 line by non-polar perturbers

Microwave spectral line widths of the transitionJ = 1 → 2 of OCS perturbed by non-polar perturbers,n-hexane, cyclohexane,n-heptane, carbon disulphide, carbon tetrachloride and benzene have been calculated using a recent theory of Mehrotra and Boggs.     

二阶偏振模色散矢量致脉冲展宽的理论分析

我们首次提出了消偏矢量的概念，并用它来描述二阶偏振模色散中偏振模色散矢量方向的变化。本文导出了由于二阶偏振模色散所引起的脉冲展宽的解析表达式，结论指出，偏振相关的本征色散总是使脉冲展宽加剧；而偏振模色散矢量方向的变化（消偏矢量），却是使脉冲展宽减弱。二阶偏振模色散对脉冲的展宽，不仅与偏振相关的本征色散和消偏矢量有关，而且还与信号的传输速率以及初始一阶偏振模色散的大小有关。信号速率的提高，将明显的使二阶偏振模色散的影响增强。在偏振相关的本征色散不为零的情况下，通过调整初始偏振态矢量、初始一阶偏振模色散矢量以及消偏矢量三者的方向，使它们互相平行，可以获得最佳的色散补偿。但是却不能获得完全的色散补偿。在最佳色散补偿时的最小脉冲展宽为σ= (2^1/2/4)( DCF/T₀).     

Multiple-scaling methods for Monte Carlo simulations of radiative transfer in cloudy atmosphere

Two multiple-scaling methods for Monte Carlo simulations were derived from integral radiative transfer equation for calculating radiance in cloudy atmosphere accurately and rapidly. The first one is to truncate sharp forward peaks of phase functions for each order of scattering adaptively. The truncated functions for forward peaks are approximated as quadratic functions; only one prescribed parameter is used to set maximum truncation fraction for various phase functions. The second one is to increase extinction coefficients in optically thin regions for each order scattering adaptively, which could enhance the collision chance adaptively in the regions where samples are rare. Several one-dimensional and three-dimensional cloud fields were selected to validate the methods. The numerical results demonstrate that the bias errors were below 0.2% for almost all directions except for glory direction (less than 0.4%) and the higher numerical efficiency could be achieved when quadratic functions were used. The second method could decrease radiance noise to 0.60% for cumulus and accelerate convergence in optically thin regions. In general, the main advantage of the proposed methods is that we could modify the atmospheric optical quantities adaptively for each order of scattering and sample important contribution according to the specific atmospheric conditions.     

Intercomparison of retrieval codes used for the analysis of high-resolution, ground-based FTIR measurements

A rigorous and systematic intercomparison of codes used for the retrieval of trace gas profiles from high-resolution ground-based solar absorption FTIR measurements is presented for the first time. Spectra were analyzed with the two widely used independent, retrieval codes: SFIT2 and PROFFIT9. Vertical profiles of O₃, HNO₃, HDO, and N₂O were derived from the same set of typical observed spectra. Analysis of O₃ was improved by using updated line parameters. It is shown that profiles and total column amounts are in excellent agreement, when similar constraints are applied, and that the resolution kernel matrices are also consistent. Owing to the limited altitude resolution of ground-based observations, the impact of the constraints on the solution is not negligible. It is shown that the results are also compatible for independently chosen constraints. Perspectives for refined constraints are discussed. It can be concluded that the error budget introduced by the radiative transfer code and the retrieval algorithm on total columns deduced from high-resolution ground-based solar FTIR spectra is below 1%.     

Line parameters for the 01111-00001 band of COO from SOIR measurements of the Venus atmosphere

CO₂ is the major constituent of the atmosphere of Venus. Absorption lines due to its ¹²C¹⁶O¹⁸O isotopologue have been observed for the first time in Venus spectra in the 2930-3015 cm⁻¹ spectral region, where the HITRAN database does not contain any line from this isotopologue. The measurements were performed by the SOIR instrument, which is part of the SPICAV/SOIR instrument on board the Venus Express mission of ESA. SOIR measured the atmospheric transmission of the upper atmosphere of Venus (z>70 km) by performing a solar occultation experiment using the atmosphere as a gigantic absorption cell. The identification of this newly observed band was first made recently from Mars atmosphere observations by US colleagues. We have made independent theoretical calculations of the positions of the lines of this new 01111-00001 absorption band, which coincide perfectly with the positions of the observed lines. Assuming an oxygen isotopic ratio similar to the one measured previously in the lower atmosphere of Venus, the line strengths of each observed line are deduced and listed.     

A solution of radiative transfer in isotropic plane-parallel atmosphere by integrating Milne equation

In this paper we solve the inversion problem of the radiative transfer process in the isotropic plane-parallel atmosphere by iterative integrations of the Milne integral equation. As a result, we obtain the scattering function in the form of a cubic polynomial in optical thickness. The author has already solved the same problem by iterative integrations of Chandrasekhar's integral equation. In the Milne integral equation, both the cosines of the viewing angles and the optical thickness are integral variables, while in Chandrasekhar's integral equation the cosines of the viewing angles are variables but the optical thickness is not. We derive several series of exponential-like functions as intermediate derivations. Their convergences are evaluated by the author's previous work in the solution of Chandrasekhar's integral equation. The truncated scattering function up to the third order in optical thickness thus obtained is identical to that obtained from Chandrasekhar's integral equation, though their apparent forms are different. Chandrasekhar pointed out that the solution of Chandrasekhar's integral equation does not have a uniqueness of solution. The Milne equation, in contrast, has been proven to have a unique solution. We discuss the uniqueness of the solution by these two methods.     

Experimental line broadening and line shift coefficients of the acetylene ν1 + ν3 band pressurized by hydrogen and deuterium and comparison with calculations

Theoretical and experimental values have been determined for the pressure broadening of the ν₁ + ν₃ band of acetylene by hydrogen and deuterium at 195 K, and experimental values of the pressure shifts have been determined. Theoretical values have been calculated on the basis of a recent potential energy surface using the close coupling scheme. We discuss the detailed contribution of the various rotational angular momenta of the perturbing gas and the ortho and para contribution to the total pressure broadening cross-sections. We give routes to circumvent the computational cost of such calculations. Experimental values have been measured using a tunable diode laser spectrometer assuming a Voigt line shape. These pressure broadening parameters are compared with measurements performed recently at room temperature and with present measurements performed at 195 K in the ν₁ + ν₃ band of acetylene. A satisfactory agreement is obtained with the present results and available ones at 295 K.