Review of quantitative spectroscopy of polyynes

We propose a review of quantitative spectroscopy of polyynes in the infrared and ultraviolet domain focusing on essential spectroscopic parameters for the interpretation of observed spectra in the infrared and ultraviolet domain and for photochemical modeling. We point at the lacking data in both wavelength domains for C₂H₂, C₄H₂, C₆H₂, C₈H₂ and propose downloadable files of the ultraviolet absorption coefficient ready to use for photolysis rate calculations. For longer polyynes, we calculate extrapolated ultraviolet spectra and calculate their photolysis rate. Using a simplified photochemical model of the polyynes in Titan and CRL618, we predict their relative abundance and compare them with the observed ones. This also leads us to predict the abundances of the longer polyynes.     

SomeL 1 existence and dependence results for semilinear elliptic equations under nonlinear boundary conditions

In this paper we study questions of existence, uniqueness, and continuous dependence for semilinear elliptic equations with nonlinear boundary conditions. In particular, we obtain results concerning the continuous dependence of the solutions on the nonlinearities in the problem, which in turn implies analogous results for a related parabolic problem. Such questions arise naturally in the study of potential theory, flow through porous media, and obstacle problems.Sponsored by the United States Army under Contract Nos. DAAG29-80-C-0041 and DAAL03-87-K-0043, and by the Air Force Office of Scientific Research under Contract No. AFOSR 84-0252 and by the National Science Foundation under Grant No. DMS-8505531. Research of the third author was carried out in part while visiting the Institute for Mathematics and Its Applications at the University of Minnesota.     

Measured integrated band intensities and simulated line-by-line spectra for 12C2HD between 25 and 2.5 μm,and new global vibration–rotation parameters for the bending vibrations

The global analysis of published high-resolution vibration–rotation spectra of ¹²C₂HD in the bending spectral range is presented, resulting in an extension of the known vibration–rotation assignments, including a new band 2v₄+v₅←2v₄ (^IΠ←Δ). Experimental integrated band intensities are reported in the range from 25 to 2.5 μm, and both v₄ and v₅ bending fundamentals are simulated line by line. An extensive line list is produced in the bending energy range, to supply previously missing information in databases.     

Frequency and intensity analyses of the far infrared ν5 band system of cyanogen (C2N2) and applications to Titan

The far infrared spectrum of cyanogen has been studied at high resolution to improve the rotational analysis of the ν₅ band system around 234 cm^?1. Present in the sample in natural abundances, both isotopologues N¹³CCN and ¹⁵NCCN have also been studied. The weak ν₄–ν₅ difference band centered at 270 cm^?1 has been studied for the first time. On the basis of a global rovibrational analysis limited to the ν₂, ν₄, and ν₅ modes, energy levels up to 2300 cm^?1 have been considered to contribute to the overall spectrum intensity at room temperature leading to a new line list of 196,994 lines. The line intensity prediction has been used to correct previous line intensity measurements by taking into account line mixing. A new vibrational transition moment has been deduced and compared to new band intensity measurements obtained by low resolution studies which are also presented in this paper. The agreement between both approaches is very good and rules out the apparent disagreement between line intensity and band intensity measurements observed in the past. An intensity study of ¹⁵NCCN is also proposed here thanks to the availability of a pure sample. Those results open the way to the search for isotopologues of cyanogen in Titan's atmosphere.     

PM3, AM1, MINDO3 semi-empirical IR spectra simulations for some nitriles of interest for Titan's chemistry

A set of the semi-empirical methods (PM3, AM1, MNDO and MINDO3) has been tested to find the best auxiliary tool for the identification of nitriles by gas chromatography/Fourier transform IR spectroscopy/mass spectrometry, considering five nitriles of interest for Titan's chemistry as test compounds: acetonitrile, acrylonitrile, cyanoacetylene, 2-butynenitrile and dicyanoacetylene. Of the four semi-empirical methods, MNDO can be considered as the most advantageous auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) identification of nitriles of interest for Titan's atmospheric chemistry, since (1) the simulated IR spectra best match the experimental (in some cases AM1 gives comparable results); (2) it provides the best linearity between the calculated and experimental frequencies (correlation coefficient of 0.990); a scaling factor of 0.90 can be applied to afford better correspondence between the calculated and experimental wavenumbers. At the same time, none of the methods is able to predict infrared intensities and a spectral intensity pattern.     

PM3, AM1, MNDO and MINDO3 semi-empirical IR spectra simulations for compounds of interest for Titan's chemistry: diazomethane, methyl azide, methyl isocyanide, diacetylene and triacetylene

Four semi-empirical methods (PM3, AM1, MNDO and MINDO3) have been tested to find the best auxiliary tool for the gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) identification of five compounds of interest for Titan's atmospheric chemistry as test compounds: diacetylene, triacetylene, diazomethane, methyl azide, methyl isocyanide. Of the four methods, MINDO3 can be considered as the most appropriate method to facilitate the identification of such and similar compounds, since (1) the simulated IR spectra best match the experimental spectra for four compounds of five studied; and (2) MINDO3 provides the best linearity between the calculated and experimental frequencies (correlation coefficient of 0.995; a scaling factor of 0.84 can be applied to afford better correspondence between the calculated and experimental wavenumbers). None of the semi-empirical methods tested is able to predict (even approximately) infrared band intensities, and therefore a spectral intensity pattern.     

Introduction

No Abstract.       

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.     

Singular limit of changing sign solutions of the porous medium equation

In this paper, we study the limit as of changing sign solutions of the porous medium equation: in a domain of , with Dirichlet boundary condition.     

Sous-solutions d'équations elliptiques dans L1

We study subsolutions for semilinear elliptic boundary value problems in L1. We consider as well nonlinear as linear boundary conditions. The nonlinear functions may be multivated. We characterize in terms of p.d.e. the subsolutions defined by a nonlinear functional analysis argument. Applications are given to obtain existence results for semilinear elliptic boundary value problems and comparison and estimates for nonlinear parabolic boundary value problems.