Mapping the growth mechanism of Ag nanoclusters in plasma-driven solution electrolysis using the PathTree method and...

The growth of metal nanoparticles in solution has been the subject of many experimental and theoretical investigations due to the great and varied utility of these particles. While previous studies have focused on very small nanoclusters and nanometer-sized particles, the intermediate steps of the growth mechanism, where few atom clusters reach their critical nucleation radius, is less well understood. We extend our recently developed PathTree method for mapping metal nanocluster growth mechanisms to include Monte Carlo propagation and generation-by-generation growth based on a dynamical reservoir of reacting species, and we apply this to study the growth of Ag nanoclusters up to 19 atoms in water. Of particular interest is the growth of these clusters under plasma-driven solution electrolysis conditions, where there is a source of solvated electrons to reduce the otherwise cationic Ag nanoclusters. We examine the effects of this reduction, the subsequent anion formation on the thermodynamically favored growth reactions using the Monte Carlo style reaction propagation and the reaction reservoir, and the effects of temperature on the Ag growth mechanism.