Systematic study of the chemical ordering in bimetallic Gold-Gold nanoparticles and the adsorption process of methyl thiol molecules on Gold-55 clusters

In this thesis we have investigated the structural evolution and their effect on the electronic and magnetic properties of bimetallic Au-Ag nanoalloys when the chemical ordering takes place, as well as the study of the adsorption of methyl-thiol molecules on Au55 cluster by using density functional theory (DFT) calculations within the generalized gradient approximation (GGA) as implemented in the SIESTA code. From different highly symmetric geometries we explored the structural evolution of all possible non-equivalent configurations at different Au-Ag concentrations for bimetallic nanoparticles (NPs) of 4, 6, 7 and 13 atoms. The most favorable structures for each cluster were obtained comparing their energetic stability through the calculation of their excess energy, linking the structure with specific features of their HOMO-LUMO gap end their total spin as the mixing takes place in each cluster. We found structural transitions from tri-dimensional geometries into planar as well as high spin values for tri-dimensional clusters up to 7 atoms. Distorted structures were obtained in almost all the 13-atom clusters. This has an important impact in their electronic and magnetic properties since the distortion highly determines the HOMO-LUMO gap and the total spin values. From all the 13-atom clusters, the most stable structures were the decahedra and the buckled bi-planar (BBP). We have also investigated the adsorption process of methyl-thiol molecules on Au55 NPs by calculating the adsorption energy for different trial configurations of SCH3-Au 55 system. Different adsorption modes were considered using the Ih symmetry of the Au cluster and taking into account the molecule orientation, as well as the rotation of the CH3 group of the molecule. Upon the adsorption we found that the molecule prefers to be adsorbed in the bridge sites, independently of their initial configuration. The atomic arrangement of the Au cluster as well as the bond lengths between Au atoms and S experience a subtle change after the adsorption process due to the strong interaction of the Au atoms in the NP surface and the S atoms of the molecule. Regarding the molecule, the bond lengths between S, C and H atoms remain the same. Besides the initial position where the molecule was placed, the orientation has an important effect on the adsorption energy and as consequence in the adsorption sites.;All our results were compared with available theoretical and experimental results for the same NPs and similar systems finding a good overall agreement.