Interaction de physisorption d'une molécule de dihydrogène avec une surface métallique

Abstract : This thesis concerns the study of the adsorption of a hydrogen molecule on various metallic surfaces and more particularly of the physisorption on silver and copper surfaces. This type of adsorption involves weak interactions of van der Waals type and takes place relatively far from the surface. To date, the accurate description of these systems (molecule physisorbed on a metal) is still a challenge. Two approaches allow obtaining a potential energy surface. The first one consists in modelling the metallic surface by a cluster and using highly correlated methods of calculation and the second one is considering the periodicity of the surface and using the density functional theory. Our objective was to couple these two approaches, which have their own advantages and their inconveniences, by using an embedding method. We have used the code VASP and the vdW-DF2 functional to obtain a potential energy surface considering 5 of the 6 degrees of freedom of the hydrogen molecule over the various surfaces. The characteristics of these potentials allowed to limit to 2 degrees of freedom (the height of the hydrogen molecule and its rotation in a perpendicular plan of the surface) for the study on clusters, which was achieved with the MOLPRO code. To check the accuracy of the potential energy surface we have compared the experimental data and the calculated ones. For that purpose, we have calculated ro-vibrational energy levels of the H2 molecule physisorbed on the various surfaces, by using the 2D potential determined with the various approaches and we have compared them with the experimental data obtained with electron energy loss spectroscopy. For the reduced systems, ro-vibrational energy levels were obtained by diagonalisation of nuclear Hamiltonian and with quantum dynamics by the Splitting method. To simulate the ro-vibrational spectrum, we calculated the dipole moment function of the system following its orientation, by the finite fields method with highly correlated methods of calculation. The embedding potential gives the closest results to experiment for the systems Cu(100)/H2 and Ag(100)/H2. On the other hand, for the system Ag(111)/H2, the potential obtained in modelling the surface by a cluster gives better results
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Eddy Bernard. Interaction de physisorption d'une molécule de dihydrogène avec une surface métallique. Chimie théorique et/ou physique. Université Paris-Est, 2016. Français. ⟨NNT : 2016PESC1089⟩. ⟨tel-01535073⟩

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