Atomistic origin of nano-silver paracrystalline structure: molecular dynamics and x-ray diffraction studies

Abstract

Classical molecular dynamics (MD) and x-ray diffraction (XRD) have been used to establish the origin of the paracrystalline structure of silver nanoparticles at the atomic scale. Models based on the face-centred cubic structure have been computer generated and their atomic arrangements have been optimized by the MD with the embedded-atom model (EAM) potential and its modified version (MEAM). The simulation results are compared with the experimental XRD data in reciprocal and real spaces, i.e. the structure factor and the pair distribution function. The applied approach returns the structural models, defined by the Cartesian coordinates of the constituent atoms. It has been found that most of the structural features of Ag nanoparticles are better reproduced by the MEAM. The presence of vacancy defects in the structure of the Ag nanoparticles has been considered and the average concentration of vacancies is estimated to be 3 at.%. The average nearest-neighbour Ag–Ag distances and the coordination numbers are determined and compared with the values predicted for the bulk Ag, demonstrating a different degree of structural disorder on the surface and in the core, compared to the bulk crystalline counterpart. It has been shown that the paracrystalline structure of the Ag nanoparticles has origin in the surface disorder and the disorder generated by the presence of the vacancy defects. Both sources lead to network distortion that propagates proportionally to the square root of the interatomic distances.