Kinetics of ligands mediated ultra-small silver cluster formation.

We discuss a kinetic mechanism that predicts different average size distributions of silver clusters with peak diameters around 0.7 nm and 1.2 nm in solution depending on the initial conditions in a redox reaction. Nanoparticle growth occurs through ligand addition and eleimination followed by irreversible dimerization and reversible ligand-monomer addition to the seed cluster. We have also incorporated the coalescence of clusters which can dominate the growth of silver nanoparticles in the presence of a strong reductant. Our calculations provide further insight into the mechanistic details of ultra-small silver cluster formation from an atomic perspective.