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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Rovibrational study of DNO3 nu5 band and collisional effect studies of CH3F microwave spectra with and without Stark effect / Etude rovibrationnelle de la bande nu5 de DNO3 et l´étude des effets collisionels dans les spectres microonde de CH3F sans et sous effet Stark

Koubek, Jindrich 15 September 2011 (has links)
Le travail qui est présenté dans ce mémoire de thèse s'inscrit dans le domaine de la Spectroscopie moléculaire en phase gazeuse théorique et expérimentale. Il comprend deux parties dédiées à des aspects relativement différents de cette discipline. La première partie présente l'analyse à haute résolution des positions et intensité des raies de la bande ν5 (ouverture angulaire du groupe NO2 dans le plan de la molécule) de DNO3 dans la région spectrale de 11 µm. Pour ce faire, nous avons utilisé un spectre infrarouge enregistré dans la région 700−1400 cm−1 à l'aide d'un spectromètre à transformée de Fourier de l'université « Bergische Universität » à Wuppertal, en Allemagne. Ce travail nous a permis de montrer que la bande ν5, centrée à 887.657 cm−1, est fortement perturbée. L'analyse prouve en effet que les niveaux d'énergie 5^1 et 7^1+9^1 sont couplés par des résonances de Coriolis de types A et B. Le schéma de résonances pour la variété isotopique DNO3 diffère donc fortement de ceux observés pour les états 5^1 et 9^2 de H14NO3 et H15NO3 qui sont majoritairement de type Fermi. Le deuxième problème abordé dans ce travail est celui des profils de raies rotationnelles pures de CH3F avec l'étude des élargissements collisionnels (collisions CH3F-CH3F et CH3F-He) des transitions optiques et de leurs composantes Stark. Des mesures microondes ont été réalisées à l'ESTC à Prague. Leur analyse a permis d'en extraire des paramètres collisionnels à l'aide de divers profils de raies (Voigt, Rautian, dépendantes de vitesse) pour les transitions J, K → J + 1, K (K = 0, …, J) avec J = 1 et J = 3 et leurs diverses composantes Stark J, K, M → J + 1, K, M' (|M| = 0, …, J ; |M − M'| = 0, 1). De plus, un modèle fondé sur l'approximation Infinite Order Sudden (IOS) a été construit pour décrire les effets d'interférences collisionnelles observés. Les résultats expérimentaux obtenus complètent et étendent des travaux précédents et sont la première démonstration de la capacité de l'approximation IOS à modéliser les couplages collisionnels entre composantes Stark / The work presented in this thesis belongs to the domain of theoretical and experimental gas phase molecular spectroscopy. It consists of two parts dedicated to two relatively different aspects in this field. The first part presents a high resolution analysis of the ν5 fundamental band (NO2 in plane bending mode) positions and intensities of D14NO3 (deuterated nitric acid) in the 11 µm spectral region. For this study, we used an infrared spectrum of D14NO3 recorded in the 700−1400 cm−1 region on a Fourier transform spectrometer at Bergische Universität in Wuppertal (Germany). Our analysis demonstrates that the fundamental ν5 band centered at 887.657 cm−1 is strongly perturbed. Indeed, it proves that 5^1 and 7^1+9^1 energy levels of DNO3 are coupled through A and B type Coriolis resonances. The resonance scheme for the isotopologue D14NO3 therefore differs substantially from the schemes of H14NO3 and H15NO3 that feature dominantly Fermi type resonances. The second theme treated in this work is devoted to the lineshapes of pure rotational transitions of CH3F with the study of collisional broadening (collisions CH3F-CH3F and CH3F-He) of optical transitions and their Stark components. The microwave measurements were realised at ICT in Prague. Their analysis enabled to provide collisional parameters using various line profiles (Voigt, Rautian, Speed dependent) for the J, K → J + 1, K (K = 0, …, J) transitions with J = 1 and J = 3 as well as for their various Stark components J, K, M → J + 1, K, M' (|M| = 0, …, J ; |M − M'| = 0, 1). Moreover, a correct use of model based on Infinite Order Sudden approximation led to very satisfactory results of the observed line-mixing effects. The retrieved experimental results complete and extend the previous studies and provide the first successful demonstration of the ability of the IOS approximation to model line-mixing effects among Stark transitions
2

Rovibrational study of DNO3 nu5 band and collisional effect studies of CH3F microwave spectra with and without Stark effect

Koubek, Jindrich 15 September 2011 (has links) (PDF)
The work presented in this thesis belongs to the domain of theoretical and experimental gas phase molecular spectroscopy. It consists of two parts dedicated to two relatively different aspects in this field. The first part presents a high resolution analysis of the ν5 fundamental band (NO2 in plane bending mode) positions and intensities of D14NO3 (deuterated nitric acid) in the 11 µm spectral region. For this study, we used an infrared spectrum of D14NO3 recorded in the 700−1400 cm−1 region on a Fourier transform spectrometer at Bergische Universität in Wuppertal (Germany). Our analysis demonstrates that the fundamental ν5 band centered at 887.657 cm−1 is strongly perturbed. Indeed, it proves that 5^1 and 7^1+9^1 energy levels of DNO3 are coupled through A and B type Coriolis resonances. The resonance scheme for the isotopologue D14NO3 therefore differs substantially from the schemes of H14NO3 and H15NO3 that feature dominantly Fermi type resonances. The second theme treated in this work is devoted to the lineshapes of pure rotational transitions of CH3F with the study of collisional broadening (collisions CH3F-CH3F and CH3F-He) of optical transitions and their Stark components. The microwave measurements were realised at ICT in Prague. Their analysis enabled to provide collisional parameters using various line profiles (Voigt, Rautian, Speed dependent) for the J, K → J + 1, K (K = 0, ..., J) transitions with J = 1 and J = 3 as well as for their various Stark components J, K, M → J + 1, K, M' (|M| = 0, ..., J ; |M − M'| = 0, 1). Moreover, a correct use of model based on Infinite Order Sudden approximation led to very satisfactory results of the observed line-mixing effects. The retrieved experimental results complete and extend the previous studies and provide the first successful demonstration of the ability of the IOS approximation to model line-mixing effects among Stark transitions

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