基于非线性最小二乘法的多光谱拟合程序：应用于12CH4谱线参数分析

精确的甲烷分子实验光谱参数在大气科学和天文探测等领域有着广泛的应用,特别是谱线的展宽系数及其温度依赖系数对于甲烷分子浓度廓线的研究尤为重要。精密的实验测量是获得准确谱线参数的重要手段。采用实验测量获取谱线参数时,需要在已知实验条件（浓度,温度,总压力,吸收光程以及气体分子种类的混合比等）的情况下,多次扫描同一波段范围得到多组实验室吸收光谱,然后利用基于非线性最小二乘法的拟合程序处理这些光谱,反演获得所需要的光谱参数。然而,一般常用的单光谱拟合程序处理实验光谱既费时又容易引起拟合过程中的误差传递。针对此问题,采用最小二乘拟合技术和Levenberg-Marquardt迭代算法编写了一款适用于处理由可调谐半导体激光吸收光谱技术（TDLAS）所获得的吸收光谱的多光谱拟合程序。该程序可同时处理多张实验光谱,并基于全局拟合方法获得一套光谱参数。详细介绍了该程序的原理、使用方法及数据处理过程。利用多光谱拟合程序中的Voigt线型处理了2 958～2 959 cm-1波数内甲烷（12CH₄）分子6条跃迁谱线的实验光谱,获得了296.0,251.0,223.0,198.0和173.0 K共5组温度下12CH₄分子6条谱线的空气展宽系数。与之前文献报道的该波段内采用单光谱拟合程序得到的相应数据对比结果表明：获得的各温度下的空气展宽系数与参考文献中相应数据差值的百分比处在-4.97%~1.58%之间,两者数据整体符合较好,并且在30组对比数据中,有4组由单光谱拟合程序得到的空气展宽系数的误差值小于由多光谱拟合程序得到的相应数值,有2组数据显示由两种方法获得的误差值相等,其余24组由多光谱拟合程序获得的数据拟合误差小于由单光谱拟合程序获得的相应数值,表明多光谱拟合程序具有良好的可靠性,适用于气体分子吸收光谱的处理。     

Line mixing effects in the ν2 + ν3 band of methane

This study provides the first direct experimental measurements of the off-diagonal relaxation matrix element coefficients for line mixing in air-broadened methane spectra for any vibrational band and the first off diagonal relaxation matrix elements associated with line mixing for pure methane in the ν₂ + ν₃ band of ¹²CH₄. The speed-dependent Voigt profile with line mixing is used with a multispectrum nonlinear least squares curve fitting technique to retrieve the various line parameters from 11 self-broadened and 10 air-broadened spectra simultaneously. The room temperature spectra analyzed in this work are recorded at 0.011 cm⁻¹ resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory, Kitt Peak, Arizona. The off-diagonal relaxation matrix element coefficients of ν₂ + ν₃ transitions between 4410 and 4629 cm⁻¹ are reported for eighteen pairs with upper state J values between 2 and 11. The observed line mixing coefficients for self broadening vary from 0.0019 to 0.0390 cm⁻¹ atm⁻¹ at 296 K. The measured line mixing coefficients for air broadening vary from 0.0005 to 0.0205 cm⁻¹ atm⁻¹ at 296 K.     

Multispectrum analysis of CH4 from 4100 to 4635 cm: 1. Self-broadening coefficients (widths and shifts)

The Lorentz self-broadening (halfwidths) and self-induced pressure-shift coefficients were measured for the first time in the octad region of methane. All spectra were recorded at 0.011 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. ¹²C-enriched CH₄ gas samples at room temperature were used, and high signal-to-noise ratios of 2000:1 were achieved. The multispectrum nonlinear least squares fitting technique enabled us to fit simultaneously a total of 10 high-resolution laboratory absorption spectra consisting of six self-broadened and four air-broadened spectra. In this paper, we report the self-broadened widths and self-induced pressure shift coefficients for 1423 transitions belonging to five bands with a maximum J of 16. The numbers of measurements by bands are: 71 for ν₂ + 2ν₄, 202 for ν₁ + ν₄, 824 for ν₃ + ν₄, 58 for 2ν₂ + ν₄, and 268 for ν₂ + ν₃. The observed widths varied from 0.045 to about 0.090 cm⁻¹ atm⁻¹ at 296 K. The measured pressure-shift coefficients had values extending from about −0.020 to −0.005 cm⁻¹ atm⁻¹ at 298.3 ± 1.2 K. The results obtained for the broadening coefficients in the various bands were compared with each other and with measurements reported in the literature for other methane bands.     

高光谱与多光谱遥感影像反演地表不透水面的对比——以Hyperion和TM/ETM+为例

不透水面遥感信息的反演是近十年来遥感领域的一个热门课题,但是利用高光谱影像反演不透水面信息的研究较少,高光谱和多光谱影像反演不透水面的对比研究也少有报道。重点研究了高光谱EO-1 Hyperion和多光谱Landsat TM/ETM+数据在反演不透水面信息方面的特点,首先在福州、广州和杭州选取了三个实验区,利用线性光谱混合分析模型反演Hyperion和TM/ETM+影像的不透水面信息。对于多达242个波段的Hyperion影像,进一步利用判别分析从中选取了11个特征波段构成新的Hyperion’影像,以考察是否可用缩减波段的方法来取得较好的反演效果。结果表明,Hyperion高光谱影像反演不透水面的能力优于多光谱影像TM/ETM+,而利用特征波段构成的Hyperion’的反演精度最高,这主要得益于Hyperion具有更高的光谱分辨率和辐射分辨率,使其可以更有效地区别不同地物在光谱特征和辐射特征上的微细变化,从而可以更好地区分不同地物。而由特征波段构成的Hyperion’影像由于大幅减少了高光谱影像波段的冗余度,所以获得了更高的反演精度。