The evolution and impact of the HITRAN molecular spectroscopic database

This note provides a brief review of the history and impact of the molecular spectroscopic database known as HITRAN (High Resolution Transmission). We reprint one of the articles describing this database (JQSRT 1998; 60: 665-710), although the series of these papers is among the most cited in the geosciences. HITRAN was established over three decades ago in response to the needs of simulating transmission in the terrestrial atmosphere, and it was enabled by new technology. However the applications of HITRAN, and the requirements on the database, have greatly expanded over the intervening years.     

The HITRAN 2004 molecular spectroscopic database

This paper describes the status of the 2004 edition of the HITRAN molecular spectroscopic database. The HITRAN compilation consists of several components that serve as input for radiative transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e., spectra in which the individual lines are unresolvable; individual line parameters and absorption cross-sections for bands in the ultra-violet; refractive indices of aerosols; tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 39 molecules including many of their isotopologues.The format of the section of the database on individual line parameters of HITRAN has undergone the most extensive enhancement in almost two decades. It now lists the Einstein A-coefficients, statistical weights of the upper and lower levels of the transitions, a better system for the representation of quantum identifications, and enhanced referencing and uncertainty codes. In addition, there is a provision for making corrections to the broadening of line transitions due to line mixing.     

HITEMP, the high-temperature molecular spectroscopic database

A new molecular spectroscopic database for high-temperature modeling of the spectra of molecules in the gas phase is described. This database, called HITEMP, is analogous to the HITRAN database but encompasses many more bands and transitions than HITRAN for the absorbers H₂O, CO₂, CO, NO, and OH. HITEMP provides users with a powerful tool for a great many applications: astrophysics, planetary and stellar atmospheres, industrial processes, surveillance, non-local thermodynamic equilibrium problems, and investigating molecular interactions, to name a few. The sources and implementation of the spectroscopic parameters incorporated into HITEMP are discussed.     

New section of the HITRAN database: Collision-induced absorption (CIA)

This paper describes the addition of Collision-Induced Absorption (CIA) into the HITRAN compilation. The data from different experimental and theoretical sources have been cast into a consistent format and formalism. The implementation of these new spectral data into the HITRAN database is invaluable for modeling and interpreting spectra of telluric and other planetary atmospheres as well as stellar atmospheres. In this implementation for HITRAN, CIAs of N₂, H₂, O₂, CO₂, and CH₄ due to various collisionally interacting atoms or molecules are presented. Some CIA spectra are given over an extended range of frequencies, including several H₂ overtone bands that are dipole-forbidden in the non-interacting molecules. Temperatures from tens to thousands of Kelvin are considered, as required, for example, in astrophysical analyses of objects, including cool white dwarfs, brown dwarfs, M dwarfs, cool main sequence stars, solar and extra-solar planets, and the formation of so-called first stars.     

Effect of the improvement of the HITRAN database on the radiative transfer calculation

The line parameters of the HITRAN 2004 have been updated, as compared with the older editions (the 2000 edition and the 1996 edition). In order to know the effect of the modifications on radiative transfer calculation with high spectral resolution, comparison in optical depth and radiance spectrum have been given between different editions. Four infrared spectral regions are selected, and they cover the three bands of atmospheric infrared sounder (AIRS) and one of geosynchronous imaging fourier transform spectrometer (GIFTS). The comparison has shown that the relative difference between HITRAN 2000 and 2004 and that between HITRAN 1996 and 2004 is decreasing. But the maximal discrepancy between the latest two editions in some spectral intervals is over 1%. It is important to estimate the error of calculation with the line parameters correctly or one has to use the new edition of HITRAN.     

The 2009 edition of the GEISA spectroscopic database

The updated 2009 edition of the spectroscopic database GEISA (Gestion et Etude des Informations Spectroscopiques Atmosphériques; Management and Study of Atmospheric Spectroscopic Information) is described in this paper. GEISA is a computer-accessible system comprising three independent sub-databases devoted, respectively, to: line parameters, infrared and ultraviolet/visible absorption cross-sections, microphysical and optical properties of atmospheric aerosols. In this edition, 50 molecules are involved in the line parameters sub-database, including 111 isotopologues, for a total of 3,807,997 entries, in the spectral range from 10⁻⁶ to 35,877.031 cm⁻¹.The successful performances of the new generation of hyperspectral sounders depend ultimately on the accuracy to which the spectroscopic parameters of the optically active atmospheric gases are known, since they constitute an essential input to the forward radiative transfer models that are used to interpret their observations. Currently, GEISA is involved in activities related to the assessment of the capabilities of IASI (Infrared Atmospheric Sounding Interferometer; http://smsc.cnes.fr/IASI/index.htm) on board the METOP European satellite through the GEISA/IASI database derived from GEISA. Since the Metop-A (http://www.eumetsat.int) launch (19 October 2006), GEISA is the reference spectroscopic database for the validation of the level-1 IASI data. Also, GEISA is involved in planetary research, i.e., modeling of Titan's atmosphere, in the comparison with observations performed by Voyager, or by ground-based telescopes, and by the instruments on board the Cassini-Huygens mission.GEISA, continuously developed and maintained at LMD (Laboratoire de Météorologie Dynamique, France) since 1976, is implemented on the IPSL/CNRS (France) “Ether” Products and Services Centre WEB site (http://ether.ipsl.jussieu.fr), where all archived spectroscopic data can be handled through general and user friendly associated management software facilities. More than 350 researchers are registered for on line use of GEISA.     

The sensitivity of radiative transfer calculations to the changes in the HITRAN database from 1982 to 2004

Over the last quarter century, improvements in the determination of the spectroscopic characteristics of the infrared-active trace species have enhanced our ability to retrieve quantitative distributions of temperatures, clouds, and abundances for various trace species within the Earth's atmosphere. These improvements have also allowed for refinements in the estimates of climatic effects attributed to changes in the Earth's atmospheric composition. Modeling efforts, however, have frequently experienced significant delays in assimilating improved spectroscopic information. Such is the case for highly parameterized models, where considerable effort is typically required to incorporate any revisions. Thus, a line-by-line radiative transfer model has been used to investigate the magnitude of the effects resulting from modifications to the spectroscopic information. Calculations from this line-by-line model have demonstrated that recent modifications to the HITRAN (High Resolution Transmission) line parameters, the continuum formulation, and the CO₂ line-mixing formulation can significantly affect the interpretation of the high spectral resolution radiance and brightness temperature retrievals. For certain moderate-resolution satellite remote sensing channels, modifications to these spectroscopic parameters and formulations have shown the capacity to induce changes in the calculated radiances equivalent to brightness temperature differences of 1-2 K. Model calculations have further shown that modifications of the spectroscopic characteristics tend to have a modest effect on the determination of spectrally integrated radiances, fluxes, and radiative forcing estimates, with the largest differences being of order 1 W m⁻² for the total thermal infrared fluxes, and of order 2-3% of the calculated radiative forcing at the tropopause attributed to the combined doubling of CO₂, N₂O, and CH₄. The results from this investigation are intended to function as a guide to differentiate between cases where older parameterizations provide acceptable results, within specified accuracy bounds, and cases where upgrades to the latest spectroscopic database are necessary.     

Effect of changes of the HITRAN database on transmittance calculations in the near-infrared region

In order to retrieve from high spectral resolution measurements with high accuracy, it is necessary to be able to evaluate the transmittance precisely. However, the uncertainty of the spectroscopic parameters is one of the most important contributions that affect the accuracy of transmittance. HITRAN is a compilation of spectroscopic parameters which has been updated several times. The transmittance calculations using the line parameters from the HITRAN’2000 database and the HITRAN’2004 database have been compared over the near infrared range from 4200 to 10,000 cm^?1. The differences between calculated transmittances over this spectral range are mainly caused by changes of the line parameters for H₂O, CO₂ and CH₄. For the tropical atmosphere, the differences are very prominent. Transmittance calculations for the sub-arctic winter atmosphere are less sensitive to the changes in the HITRAN database than those for the tropical atmosphere; but, the changes of line parameters still can not be ignored when considering the relative differences. For example, the relative difference is ～35% at 5073.3 cm^?1 with 0.2 cm^?1 spectral resolution. The comparisons have shown that it is important to pay attention to the changes of line parameters of the HITRAN database or to use the latest edition so as to improve the accuracy of atmospheric sounding with high spectral resolution.     

Revised ultraviolet absorption cross sections of H2CO for the HITRAN database

A revised set of temperature-dependent absorption cross sections for ultraviolet (UV) measurements of formaldehyde (H₂CO) has been derived from two existing sets of laboratory cross sections, one using a Fourier transform spectrometer (FTS), and one using a grating instrument. This is conducted to satisfy the recommendation of the HITRAN Advisory Committee to provide a dataset with the spectral resolution and wavelength calibration of Fourier transform spectrometer measurements with the better intensity calibration that the grating measurements obtained. The re-scaled cross sections are now in the HITRAN database, and are recommended for use in atmospheric measurements and modeling, including photolysis calculations.     

The 2003 edition of the GEISA/IASI spectroscopic database

The content of the current (2003) version, GEISA/IASI-03, of the computer-accessible spectroscopic database, GEISA/IASI, is described. This “system” or database is comprised of three independent spectroscopic archives, which are (a) a database of individual spectral line parameters on 14 molecules, H₂O, CO₂, O₃, N₂O, CO, CH₄, O₂, NO, SO₂, NO₂, HNO₃, OCS, C₂H₂, N₂, and the related 51 isotopomers and isotopologues, representing 702,550 entries, in the spectral range 599-, (b) a database of spectral absorption cross-sections (6,572,329 entries related to six molecules, CFC-11, CFC-12, CFC-14, HCFC-22, N₂O₅, CCl₄), and a catalogue of microphysical and optical properties (mainly, the refractive indices) of atmospheric aerosols. The modifications and improvements, which have been implemented since the earlier editions of this database, in terms of content and management, have been explained in detail. GEISA/IASI has been created with the specific purpose of assessing the capability of measurement by the IASI instrument within the designated goals of ISSWG in the frame of the CNES/EUMETSAT European Polar System preparation.All the archived data can be handled through a user-friendly associated management software, which is posted on the ARA/LMD group web site at http://ara.lmd.polytechnique.fr.     

The identification of nonlinear molecular systems by spectroscopic methods

The Wiener functional expansion method for the analysis of nonlinear systems is applied to identify and analyze both nonlinear and linear molecular systems by spectroscopic methods. As the sampling filter (monochromator) of any spectroscopic apparatus may be defined by a Weber-Hermite polynomial, an analysis of the refracted or scattered light by orthogonal polynomials is easily achieved. Time averaging obtains the Weber-Hermite coefficients which permit the characterization of the molecular system with respect to the polarization of the incident and scattered light. In the case of two series of measurements made with incident and emerging light polarized in different directions: the identification of the JonesM matrices for the molecular system irradiated is possible. In the case of three series of measurements made, for example, with incident and emerging light (a) circularly polarized corotating, (b) circularly polarized contrarotating, and (c) plane polarized perpendicular: the identification of the molecular system's McClain invariants related to the vibrational symmetry group for Raman inelastic light scattering is possible. The analysis presents a unified picture of elastic and inelastic light scattering and one-photon and two-photon processes. The apparatus described would detect those instances in molecular systems for which Beer's law does not apply.     

Extracting molecular potentials from incomplete spectroscopic information

We extend our recently developed inversion method to extract excited-state potentials from fluorescence line positions and line strengths. We consider a previous limitation of the method arising due to insufficient input data in cases where the relatively weaker emission data are not experimentally available. We develop a solution to this problem by ‘regenerating’ these weak transition lines via applying a model potential, e.g. a Morse potential. The result of this procedure, illustrated for the Q-branch emission from the lowest three vibrational levels of the B(¹Π) state of LiRb, is shown to have an error of 0.29 cm^?1 in the classically allowed region and a global error of 5.67 cm^?1 for V ≤ E(ν′ = 10). The robustness of this procedure is also demonstrated by considering the statistical error in the measured line intensities.     

The GEISA spectroscopic database: Current and future archive for Earth and planetary atmosphere studies

The development of Gestion et Etude des Informations Spectroscopiques Atmosphériques (GEISA: Management and Study of Spectroscopic Information) was started over three decades at Laboratoire de Météorologie Dynamique (LMD) in France. GEISA is a computer accessible spectroscopic database, designed to facilitate accurate forward radiative transfer calculations using a line-by-line and layer-by-layer approach. More than 350 users have been registered for on-line use of the GEISA facilities. The current 2003 edition of GEISA (GEISA-03) is a system comprising three independent sub-databases devoted respectively to: line transition parameters, infrared and ultraviolet/visible absorption cross-sections, microphysical and optical properties of atmospheric aerosols.Currently, GEISA is involved in activities related to the assessment of the capabilities of IASI (Infrared Atmospheric Sounding Interferometer on board of the METOP European satellite) through the GEISA/IASI database derived from GEISA.The GEISA-03 content is presented, placing emphasis on molecular species of interest for Earth and planetary atmosphere studies, with details on the updated 2008 archive underway. A critical assessment on the needs, in terms of molecular parameters archive, related with recent satellite astrophysical missions is made. Detailed information on free on-line GEISA and GEISA/IASI access is given at http://ara.lmd.polytechnique.fr and http://ether.ipsl.jussieu.fr.     

New assignments, line intensities, and HITRAN database for CH3OH at 10 μm

The Fourier transform spectrum of CH₃OH in the 10 μm region has been re-examined at higher pressure and path length than heretofore, as part of a program to provide comprehensive CH₃OH spectral data for astrophysical and atmospheric applications. With the increase in spectral sensitivity, it has been possible to assign new torsionally excited ν₁₂=1 and ν₁₂=2 subbands plus further high-K, ν₁₂=0 subbands of the ν₈ CO-stretching band. Upper-state term values have been determined, and have been fitted to J(J+1) power-series expansions in order to obtain the excited ν₈ substate origins. A variety of weaker subbands from other modes has also been identified in the 10 μm spectrum including ν₁₂=0, ν₁₂=1, and ν₁₂=0←1 torsional subbands of the ν₇ in-plane CH₃ rock, ν₁₂=0←1 and ν₁₂=0←2 torsional combination subbands of the ν₆ OH bend, and ν₁₂=0←2 subbands of the ν₅ symmetric CH₃ bend. Line intensities have been retrieved line-by-line from the spectra. A large set of “unperturbed” ν₈ transitions has been modeled using the same type of multi-parameter effective Hamiltonian employed successfully for the ground state, with inclusion of the intensities of a subset of the stronger ν₈ spectral lines in the fitting in order to obtain appropriate transition dipole terms. Together, a 10 μm methanol database in HITRAN format has been generated.     

The impact of several atomic and molecular laser spectroscopic techniques for chemical analysis

Several laser-based methods, namely laser induced fluorescence, laser enhanced ionisation and thermal lensing spectrophotometry are discussed with respect to their capabilities of approaching the extremely high detection sensitivity which is nowadays required in many fields of application, notably in high purity materials, in biomedicine and in the nuclear industry. The discussion is restricted to atomisers operated at atmospheric pressure, i.e., combustion flames, plasmas and graphite furnaces. It is shown that the analytical limit of detection can be in the range of femtograms and that double-resonance excitation possesses significant advantages over single-resonance excitation, both in terms of signal-to-noise ratio and spectral selectivity. In addition, the combination of the fluorescence and ionisation techniques represents a remarkable diagnostic tool. In the nuclear field, the suitability of the technique of thermal lensing for the direct determination and chemical speciation of very low levels of uranium in water is discussed.     

MgH分子低激发态的光谱和分子常数

利用Davidson修正的内收缩多参考组态相互作用(MRCI+Q)方法,结合相关一致全电子基aug-cc-pwCV5Z优化计算了MgH分子5个低激发电子态(5Λ–S)的势能曲线. 为了得到高精确的光谱性质,计算中引入核价电子相关和相对论效应修正. 利用LEVEL8.0程序拟合修正的Λ-S束缚态的势能曲线,得到了相应的光谱常数、振动能级和分子常数,结果与近来的理论计算相比,本文的数值更接近实验值. 这些结果说明高精度的计算方法和引入相关修正对分析光谱性质是非常必要的,为进一步研究MgH分子高激发态的光谱和跃迁特性提供可靠的实验和理论参考.     

MgH分子低激发态的光谱和分子常数

利用Davidson修正的内收缩多参考组态相互作用(MRCI+Q)方法,结合相关一致全电子基aug-cc-pw CV5Z优化计算了MgH分子5个低激发电子态(5Λ–S)的势能曲线.为了得到高精确的光谱性质,计算中引入核价电子相关和相对论效应修正.利用LEVEL8.0程序拟合修正的Λ-S束缚态的势能曲线,得到了相应的光谱常数、振动能级和分子常数,结果与近来的理论计算相比,本文的数值更接近实验值.这些结果说明高精度的计算方法和引入相关修正对分析光谱性质是非常必要的,为进一步研究MgH分子高激发态的光谱和跃迁特性提供可靠的实验和理论参考.     

基于HITRAN光谱数据库的TDLAS直接吸收信号仿真研究

对TDLAS直接吸收信号进行仿真研究,能够充分了解TDLAS直接吸收的过程以及各个物理参量的变化对吸收信号的影响。首先全面研究分析了TDLAS直接吸收方法的理论基础及算法,给出了基于朗伯-比尔定率的气体吸收线强、吸收截面、浓度、线型函数以及气体总体配分函数等参量的表达式及计算步骤。基于HITRAN光谱数据库,利用MATLAB程序对TDLAS直接吸收过程进行了仿真,计算得到了一定温度、压力、浓度等条件下的吸收谱数据。以H₂O为研究对象,仿真了其在各个线型下的吸收谱,并与商用软件Hitran-PC的结果进行比较,结果显示两者在Lorentz线型下的最大误差小于0.5%,在Gauss线型下的最大误差小于2.5%,在Voigt线型下的最大误差小于1%,因此验证了仿真算法及结果的正确性。还对不同压力和温度下ν₂+ν₃谱带H₂O的吸收谱进行了仿真,研究了吸收谱随压力和温度变化规律。在低压范围,多普勒展宽占主导,线宽随压力变化很小,而幅度随压力增大而增大,在高压范围,碰撞展宽占主导,线宽随压力增大而增大,而幅度则随压力增大而趋于定值。最后还给出了大气环境温度范围内的温度修正曲线。该研究可以为TDLAS直接吸收方法的实际应用提供理论参考和指导。