1,721,038 research outputs found
Infrared and Raman spectroscopy at very high resolution of the ethylene molecule
No full textLa spectroscopie est un outil puissant et non-destructif permettant, d’après les spectres, de remonter à des grandeurs physiques importantes telles que la concentration, la température, la pression, … du gaz en question.Les travaux présentés dans ce manuscrit sont consacrés à l’analyse des spectres infrarouges et Raman à très haute résolution de l’éthylène pour des applications atmosphériques et planétologiques.Cette thèse a été effectuée au sein du Groupe de Spectrométrie Moléculaire et Atmosphérique (GSMA) de l’Université de Reims Champagne- Ardenne. En collaboration avec l’équipe (SMPCA) au sein du laboratoire Interdisciplinaire Carnot de Bourgogne (ICB) à Dijon, l’équipe (CQP) au sien du service de Chimie Quantique et Photophysique à Bruxelles, l’Instituto de Estructura de la Materia (CSIC) à Madrid et les membres de la ligne AILES du centre de rayonnement synchrotron SOLEIL à Saint-Aubin.Cette thèse est structurée en 4 chapitres. Le premier chapitre est consacré sur les généralités de la molécule étudiée. Le second chapitre présente l’aspect théorique de la spectroscopie. Le troisième chapitre portant sur l’explication du modèle théorique qui nous avons utilisé pour effectuer l’analyse et le traitement des spectres. Dans le quatrième chapitre, nous présentons les résultats de l’analyse du spectre de la molécule de l’éthylène en différentes régions spectral.Ces résultats alimenteront des bases de données internationales telles que HITRAN (L. Rothmann) et GEISA (M. Rotger et le CNES) mais aussi peuvent servir de données modèle pour la start-up AEROVIA initiée par G. Durry, directeur de notre laboratoire. Avec ces données, nous alimenterons également la base de données européenne VAMDC.The spectroscopy is a powerful analytical technique capable of providing Important Information physical quantities such as concentration, temperature, pressure, ... and other questions about gas.The work presented in this manuscript is devoted to analysis of high resolution infrared and Raman spectroscopy of the ethylene for atmospheric, astrophysical and planetological applications.The work described in this thesis was performed within the "Groupe de Spectrométrie Moléculaire et Atmosphérique" (GSMA) in the university of Reims Champagne-Ardenne in Reims. In national collaboration with the team (SMPCA) In collaboration in the laboratory "Interdisciplinaire Carnot de Bourgogne" (ICB) in Dijon, the team (CQP) in the service de "chimie quantique et photophysique" in Brussels. l’Instituto de Estructura de la Materia (CSIC) in Madrid and the members of the line AILES of the Synchrotron SOLEIL in Saint-Aubin.The thesis is structured into 4 main chapters. The first chapter deals with the generality of molecule studied. The second chapter represents the theoretical aspects of the spectroscopy. The third chapter dealing with the explanation of the theoretical model that we used for the analysis and processing of spectra. In the fourth chapter, we present the results of the analysis of the spectrum of the molecule of ethylene in different spectral regions.These results will feed the international databases such as HITRAN (L. Rothmann) and GEISA (Mr. Rotger and CNES), and it can also serve as a data for modeling the start-up AEROVIA initiated by G. Durry, the director of the laboratory. with these data, we can also feed the European database VAMDC
Rovibrational spectroscopy of ethylene : Stark effect : Application to ethylene in zeolites
No full textL’objectif de ce mémoire est de présenter une étude aussi complète que possible de l’effet Stark dans les toupies asymétriques de type X2Y4 possédant le groupe de symétrie D2h et de l’appliquer au problème de la spectroscopie de l’éthylène piégé dans une zéolithe. Pour la première fois, un formalisme tensoriel adapté à l’étude de l’effet Stark pour la chaine de groupes O(3) D2h a été développé. Parallèlement au développement du modèle théorique, des programmes informatiques ont été mis au point sous la forme d’une nouvelle génération de logiciel appelé D2hTDS-ST utilisant une base plus simple, permettant une économie en temps de calcul. Sur la base des outils théoriques et informatiques ainsi qu’à partir des spectres expérimentaux enregistrés au laboratoire, nous avons fait une première estimation de la valeur du champ électrique effectif moyen produit par la silicalite-1. Les valeurs du champ électrique obtenues avec notre méthode sont cohérentes avec les valeurs obtenues par les calculs ab initio PBE1PBE6-31++G(2d,2p).The objective of this report is to present a study as complete as possible of the Stark effect in the asymmetric top molecules of X2Y4 type possessing the D2h symmetry group and to apply it to the problem of the spectroscopy of the ethylene molecule trapped in a zeolite. For the first time, a tensorial formalism adapted to the study of the Stark effect for the O(3) D2h group chain was developed. In parallel, a computer package was worked out as a new generation of software called D2hTDS-ST using a simpler basis, allowing an economy in the calculation time. On the basis of the theoretical and computing tools as well as from the experimental spectra, recorded in the laboratory, we made a first estimation of the average effective electric field produced by silicalite-1. The values of the electric field obtained with our method are coherent with the values obtained by the ab initio PBE1PBE6-31++G(2d,2p) calculations
Contribution and limitation of infrared spectroscopy technique to understand physisorption processes on MFI zeolites
No full textCe mémoire traite de l’apport expérimental de la spectroscopie infrarouge à la compréhension des processus d’adsorption mis en jeu au cours de l’interaction d’un gaz pur avec un matériau nanoporeux. Le travail concerne plus particulièrement une étude fondamentale de l’adsorption de l’éthylène, du trichloroéthylène, du tétrachloroéthylène, de l’hexafluorure de soufre et du p-xylène sur des zéolithes MFI, notamment la silicalite-1. La première étape de ce travail de thèse a consisté à mettre au point un nouveau dispositif expérimental et une méthode d’analyse afin d’acquérir des données d’absorption infrarouges fiables tout en améliorant les performances du prototype réalisé dans le cadre d’études antérieures. L’un des apports majeurs de ce travail est de pouvoir suivre, pour la première fois, semble-t-il, l’évolution des bandes de structure de la zéolithe au cours du processus d’adsorption. De plus, dans le cas particulier de l’adsorption du trichloroéthylène, du tétrachloroéthylène ou du p-xylène, le spectre infrarouge de la zéolithe subit de profondes modifications au cours de l’accumulation des molécules dans la microporosité du matériau. Ces modifications qui se manifestent par sauts successifs à des remplissages déterminés, ont été corrélées aux changements de structure de l’adsorbant mis en évidence par ailleurs par d’autres techniques expérimentales. Un autre point fort de ce travail concerne la caractérisation de la phase adsorbée tout au long du processus d’adsorption. D’une façon générale, le confinement des molécules dans la microporosité de la zéolithe induit essentiellement de faibles modifications de la position des bandes de vibration du fluide adsorbé, de l’ordre de quelques cm-1, sans en affecter pour autant leur allure. L’aire de ces bandes augmente proportionnellement avec la charge, dans le cas de l’adsorption de l’éthylène, du trichloroéthylène ou de l’hexafluorure de soufre. En revanche, cette relation de proportionnalité n’est plus vérifiée dans le cas de l’adsorption du tétrachloroéthylène ou du p-xylène. Pour ces systèmes avec lesquels ont été observées des isothermes à sous marche, l’aire des bandes de la phase adsorbée reste constante, en particulier dans le domaine de remplissage compris entre 3 et 6 moléc.maille-1. L’hypothèse de la formation de dimères est avancée pour rendre compte de cette singularité dans ce domaine de remplissage.This manuscript is devoted to the study of adsorption processes by FTIR spectroscopy. The experimental results concern the adsorption of ethylene, trichloroethylene, tetrachloroethylene, sulfur hexafluoride or p-xylene on MFI zeolites, more especially on silicalite-1. The first step of the work was to develop a new experimental device and procedure in order to obtain reliable absorption infrared data and to improve results previously obtained by a prototype. The first main result is to characterize, maybe for the first time, the evolution of the spectrum of the adsorbent all during the adsorption process. Experiments reveal that the zeolite infrared spectrum undergoes strong modifications when trichloroethylene, tetrachloroethylene or p-xylene molecules are adsorbed. These modifications have been correlated to adsorbent phase transitions characterized elsewhere by other experimental techniques. Another main result concerns the characterisation of the adsorbed phase during the accumulation of molecules in the zeolite. From a general point of view, the confinement of admolecules inside microporosity induces small shifts of vibrational bands of the adsorbed phase without significant modification of their shape. In contrast, the area of these bands depends on the nature and the number of adsorbed molecules. Indeed, it linearly increases with loading for the adsorption of ethylene, sulfur hexafluoride or trichloroethylene. On the contrary, when stepped isotherms are obtained, that is the case for tetrachloroethylene or p-xylene adsorption, the area of these bands stay constant within a filling domain 3-6 molec.(u.c)-1. The assumption of the formation of dimeric structures is proposed to explain such a singular behaviour
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Global frequency and intensity analysis of the V10/V7/V4/V12 bands system of 12C2H4 at 10 μm using the D2H top data system
Get PDF"A global frequency and intensity analysis of the infrared tetrad located in the cm region was carried out using the tensorial formalism developed in Dijon for XY asymmetric-top molecules\footnote{Raballand W, Rotger M, Boudon V, Lo{\""e}te M. J Mol Spectrosc 2003"217:239--48.} and a program suite called (now part of the XTDS/SPVIEW spectroscopic software)\footnote {Wenger Ch, Boudon V, Rotger M, Champion JP, Sanzharov M. J Mol Spectrosc 2008251:102--13.}. It relied on spectroscopic information available in the literature and retrieved from absorption spectra recorded in Brussels using a Bruker IFS 120 to 125 HR upgraded Fourier transform spectrometer, in the frame of either the present or previous work\footnote{Rotger M, Boudon V, Vander Auwera J. J Quant Spectrosc Radiat Transf 2008109:952-62.}. In particular, 645 and 131 lines intensities have been respectively measured for the weak and bands. Including the Coriolis interactions affecting the upper vibrational levels , , and , a total of 10737 line positions and 1870 line intensities have been assigned and fitted with global root mean square deviations of cm and {2.4} \%, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65420 lines in the , , and bands of CH was generated. The present work provides an obvious improvement over HITRAN and GEISA for the band (see figure), and a marginally better modeling for the band (and for the band hidden beneath it). To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum.Made available in DSpace on 2017-01-26T21:39:52Z (GMT). No. of bitstreams: 3
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Previous issue date: 2016-06-2
Global frequency and intensity analysis of the V10/V7/V4/V12 bands system of 12C2H4 at 10 μm using the D2H top data system
No full textA global frequency and intensity analysis of the infrared tetrad located in the cm region was carried out using the tensorial formalism developed in Dijon for XY asymmetric-top molecules\footnote{Raballand W, Rotger M, Boudon V, Lo{\"e}te M. J Mol Spectrosc 2003217:239--48.} and a program suite called (now part of the XTDS/SPVIEW spectroscopic software)\footnote {Wenger Ch, Boudon V, Rotger M, Champion JP, Sanzharov M. J Mol Spectrosc 2008251:102--13.}. It relied on spectroscopic information available in the literature and retrieved from absorption spectra recorded in Brussels using a Bruker IFS 120 to 125 HR upgraded Fourier transform spectrometer, in the frame of either the present or previous work\footnote{Rotger M, Boudon V, Vander Auwera J. J Quant Spectrosc Radiat Transf 2008109:952-62.}. In particular, 645 and 131 lines intensities have been respectively measured for the weak and bands. Including the Coriolis interactions affecting the upper vibrational levels , , and , a total of 10737 line positions and 1870 line intensities have been assigned and fitted with global root mean square deviations of cm and {2.4} \%, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65420 lines in the , , and bands of CH was generated. The present work provides an obvious improvement over HITRAN and GEISA for the band (see figure), and a marginally better modeling for the band (and for the band hidden beneath it). To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum
Dispelling the Myths Behind First-author Citation Counts
Get PDFWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
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