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No / We report a numerical calculation of the melting point of NaCl. The solid-liquid transition was located by determining the point where the chemical potentials of the solid and liquid phases intersect. To compute these chemical potentials, we made use of free energy calculations. For the solid phase the free energy was determined by thermodynamic integration from the Einstein crystal. For the liquid phase two distinct approaches were employed: one based on particle insertion and growth using the Kirkwood coupling parameter, and the other involving thermodynamic integration of the NaCl liquid to a Lennard-Jones fluid. The latter approach was found to be significantly more accurate. The coexistence point at 1074 K was characterized by a pressure of -30+/-40 MPa and a chemical potential of -97.9+/-0.2kßT. This result is remarkably good as the error bounds on the pressure enclose the expected coexistence pressure of about 0.1 MPa (ambient). Using the Clausius-Clapyron relation, we estimate that dP/dT~3 MPa/K. This yields a melting point of 1064+/-14 K at ambient pressure, which encompasses the quoted range for the experimental melting point (1072.45-1074.4 K). The good agreement with the experimental melting-point data provides additional evidence that the Tosi-Fumi model for NaCl is quite accurate. Our study illustrates that the melting point of an ionic system can be calculated accurately by employing a judicious combination of free energy techniques. The techniques used in this work can be directly extended to more complex, charged systems.

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Hydrated cement paste (HCP), which is present in various cement-based materials, includes a number of constituents with distinct nano-structures. The elastic properties of the HCP crystals are calculated using molecular dynamics (MD) methods. The accuracy of estimated values is verified by comparing them with the results from experimental tests and other atomistic simulation methods. The outcome of MD simulations is then extended to predict the elastic properties of the C-S-H gel by rescaling the values calculated for the individual crystals. To take into account the contribution of porosity, a detailed microporomechanics study is conducted on low- and high-density types of C-S-H. The obtained results are verified by comparing the rescaled values with the predictions from nanoindentation tests. Moreover, the mechanical behavior of the HCP crystals is examined under uniaxial tensile strains. From the stress-strain curves obtained in the three orthogonal directions, elastic and plastic responses of the HCP crystals are investigated. A comprehensive chemical bond and structural damage analysis is also performed to characterize the failure mechanisms of the HCP crystals under high tensile strains. The outcome of this study provides detailed information about the nonlinear behavior, plastic deformation, and structural failure of the HCP phases and similar atomic structures.

Dans ce travail, nous avons étudié l’adsorption dissociative de l’hydrogène sur Pd(111) ainsi que la diffusion d’un atome de l’hydrogène sur ce même surface. A l’aide de la théorie de la fonctionnelle de la densité, nous avons mené une étude systématique de l’effet du recouvrement en surface sur l’énergétique de la dissociation de H2 sur une surface de Pd(111) couverte par des atomes de l’hydrogène. Un résultat surprenant que nous avons trouvé est que les atomes adsorbés ont non seulement un effet de poison mais peuvent aussi promouvoir la dissociation de H2 s’ils sont adsorbés sur des sites loin de la molécule d’hydrogène qui dissocie. En ce qui concerne la diffusion d’un atome d’ hydrogène sur Pd(111), nous avons déterminé le coefficient de diffusion par des simulations de dynamique moléculaire en utilisant la formule d’Einstein à différente température de la surface, Ts=500K, 300K and 250K. Une méthode de la dynamique moléculaire accélérée a été développée afin d’étudier la diffusion à bases températures. Dans notre approche, l’accélération se fait moyennant l’augmentation de l’énergie cinétique de l’atome qui diffuse suivant une distribution Maxwell-Boltzmann qui correspond à une température plus élevée et la correction de l’échelle de temps d’une façon consistante. Pour tester la validité de notre approche, nous avons effectué des simulations pour la diffusion d’un atome d’hydrogène sur Pd(111) à Ts=300K and Ts=100K. Les résultats obtenus par la méthode accélérée est en bon accord avec ceux de la simulation standard. Par la méthode accélérée, l’échelle de temps peut être étendu à l’ordre de micro-secondes. / In this thesis, we studied dissociative adsorption of hydrogen on Pd(111) with particular attention paid to the surface coverage effect and the diffusion of a hydrogen adatom on Pd(111). With the help of DFT calculations, we carried out a systematic investigation of the effect of H-adatoms on the dissociation energetics of H2 on H-covered Pd(111) surfaces at various coverages. A quite surprising finding is that the H-adatoms do not only have a poisoning effect but can also promote H2 dissociation when they are adsorbed on sites which are sufficiently far from the dissociating H2 molecule. The macroscopic diffusion coefficient of an H-adatom on Pd(111) is determined from molecular dynamics simulations with the help of Einstein formula for different surface temperatures, i.e., Ts=500K, 300K and 250K. An accelerated molecular dynamics method was developed in order to study the diffusion at low surface temperatures. In our approach, the acceleration is achieved by increasing the kinetic energy of the diffusing atom according to the Maxwell-Boltzmann distribution at a higher temperature and correcting the time scale in a consistent way. For testing the validity of our method, we performed simulations for the diffusion of H adatom on Pd(111) surface at T=300K and T=100K. The diffusion coefficient obtained from the accelerated MD method is in agreement with that obtained from the direct MD and TST methods. And the physical time scale can be extended to the order of microseconds.

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