A systematic computational study of the structure crossover and coordination number distribution of metallic nanoparticles

In this study, we identified stable configurations for three nanoparticle structure motifs (icosahedral, decahedral and cuboctahedral) of eight transition metals (Cu, Ag, Au, Pd, Ni, Rh, Ir, and Pt) ranging in size from 140 to 3000 atoms. We made simple yet precise analytical approximations of the energy of the stable configurations as a function of nanoparticle size and calculated the structure crossover sizes from these approximations. We then analyzed the surface structure of the nanoparticles in terms of the distribution of the coordination numbers and active sites. We found that low-coordinated atoms are most preferable for cuboctahedral forms and for lighter metals - Cu, Ni and Rh. Compared to other considered metals, gold nanoparticles exhibited unique features as follows: the least amount of low-coordinated atoms, the largest fraction of (111) faces on its surface and a concave reconstruction of five-fold vertices.