Dans cette these, nous avons effectue l'analyse des spectres d'absorption a haute resolution de H2S, D2S, HDS et SO2 enregistres pour la premiere fois ou avec une meilleure precision experimentale que les spectres anterieurs. Nous avons developpe une methode originale de "global ftting" qui nous a permis l'analyse de 22 bandes vibrationnelles soit un total de 9700 transitions rovibrationnelles pour la molecule de D2S. Nous avons applique cette meme methode a des molecules de symmetrie Cs, en particulier tout le spectre rovibrationnel de la molecule HDS a ete analyse. La methode SPGF est appliquee aux molecules triatomiques H2S, D2S, HDS. Une procedure originale permettant l'identication des bandes tres peu intenses a ete mise au point pour la premiere fois et appliquee aux bandes chaudes de la molecule SO2. Le formalisme U(p+1) est adapte aux molecules triatomiques non lineaires de symmetrie C2v et les parametres d'un Hamiltonien vibrationnel sont determines dans le cas de la molecule D2S.

Most research on confirmatory factor analysis using global fit indices (AIC, BIC, AICc, and CAIC) has been in the structural equation modeling framework. Little research has been done concerning application of these indices to item response models, especially within the framework of multidimensional Rasch analysis. The results of two simulations studies that investigated how sample size, between-dimension correlation, and test length affect the accuracy of these indices in model recovery using a multidimensional Rasch analysis are described in this dissertation. The first study analyzed dichotomous data, with model-to-data misfit as an additional independent variable. The second study analyzed polytomous data, with rating scale structure as an additional independent variable. The interaction effect between global fit index and between-dimension correlation had very large effect sizes in both studies. At higher values of between-dimension correlation, AIC indicated the correct two-dimension generating structure slightly more often than does the BIC or CAIC. The correlation by test length interaction had an odds ratio indicating practical importance in the polytomous study but not the dichotomous study. The combination of shorter tests and higher correlations resulted in a difficult-to-detect distinction being modeled with less statistical information. The correlation by index interaction in the dichotomous study had an odds ratio indicating practical importance. As expected, the results demonstrated that violations of the Rasch model assumptions are magnified at higher between-dimension correlations. Recommendations for practitioners working with highly correlated multidimensional data include creating moderate length (roughly 40 items) instruments, minimizing data-to-model misfit in the choice of model used for confirmatory factor analysis (MRCMLM or other MIRT models), and making decisions based on multiple global indices instead of depending on one index in particular. / Ph. D.

L’assemblage couche-par-couche permet de fabriquer des films multimatériaux aux propriétés variées présentant une structure stratifiée. Ce travail décrit les études structurelles des films multicouches de polyélectrolytes à l’aide de mesures de diffusion de neutrons.L’effet du vieillissement des films a été déterminé par réflectométrie des neutrons. Nous avons observé un léger tassement des films après 5 ans et une forte expansion après 15 ans.Nous avons aussi montré que le substrat et l’air en surface ont une influence sur la structure des couches proches des extrémités des films, conduisant à une structure inhomogène perpendiculairement à la surface.Nous avons finalement étudié la conformation des chaînes de polyélectrolytes dans les films multicouches ; nous avons déterminé que les chaînes de PSS dans des films préparés par trempage ont une conformation en pelotes aplaties, contrairement aux chaînes de polyélectrolytes en solution qui présentent une conformation sphérique. / The Layer-by-Layer assembly allows the build-up of multimaterial films with various properties showing a stratified structure. This work describes the structural strudies of multilayer films of polyelectrolytes with neutron scattering measurements.Ageing effect on films was determined by neutron reflectometry. We observed a slight shrink of the films after 5 years and a strong expansion after 15 years.We also showed that the proximity of the substrate and the air at the surface have an influence on the structure of the layers at the extremities of the films, leading to an inhomogeneous structure perpendicularly to the surface.Finally, we studied the conformation of polyelectrolyte chains in the multilayer films ; we determined that PSS chains in dipped films have a flattened coil conformation, whereas the polyelectrolyte chains in solution have a spherical conformation.