24 research outputs found

    Origins of Negative Gas Adsorption

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    International audienceNegative gas adsorption by a porous crystalline solid, DUT-49, observed by spontaneous desorption of gas during a pressure increase raises fundamental questions on the physical origin of this puzzling behavior. Importantly, a framework that can transform a large amount of strain into pressure has many possible technological applications. To address this question, we studied the mechanics and thermodynamics of DUT-49 at both the molecular unit and framework scales by applying quantum density functional theory and extensive classical molecular-dynamics simulations. We demonstrate that negative gas adsorption originates from molecular buckling of the organic structural unit and thus allows a colossal framework transformation. Methane adsorption is subsequently shown to activate this transition, in full agreement with experimental observations. The molecular insight presented here unveils the mechanics and thermodynamics responsible for negative gas adsorption and provides unparalleled understanding to aid the discovery of new examples of similarly responsive porous metamaterials

    Modélisation numérique et assimilation de données de la dispersion de radionucléides en champ proche et à l'échelle continentale

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    La justification de l'application de l'assimilation de données à la dispersion de radionucléides découle de la confrontation de modèles aux observations. En champ proche, l'approche variationnelle standard a permis de coupler l'adjoint du modèle de dispersion, pX 0.1, et des mesures collectées dans une soufflerie. Le débit de la source a été inversé. L'optimisation des paramètres de forçage, qui gouverne la forme géométrique du panache, a amélioré l'accord entre les mesures et le modèle. La réduction des réseaux de mesures a été abordée. A l'échelle continentale, la méthode du maximum d'entropie a été utilisée pour reconstruire des sources. Des nouvelles fonctions coût, adaptées au problème, ont été construites. Leur performance a été illustrée sur une série des mesures synthétiques, parfaites et bruitées, générées par le modèle POLAIR 3D. Une méthode opérationnelle de réduction des sites suspectés a été testée. Le profil temporel de la source de l'incident d'Algéciras a été inversé.Model-to-data comparisons justify using data assimilation in dispersion of radionuclides. Near-field measurements collected in a wind tunnel experiment have been coupled to an adjoint of the dispersion model, pX 0.1. Standard variational data assimilation let invert activity rate. Forcing parameters that define the geometric form of the plume, have been optimised and a better model-to-data agreement has been achieved. Reduction of measurement networks has been tackled. At continental scale, the maximum entropy method has been used to invert sources of accidental releases. New, problem-adapted cost functions have been derived. They have been tested on twin experiments using perfect or noisy measurements that have been generated by POLAIR 3D. An operationally useful method of reducing the number of suspected sites has been shown. The temporal profile of the source of Algeciras incident has been inverted.PARIS12-CRETEIL BU Multidisc. (940282102) / SudocSudocFranceF
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