Excess thermal energy and latent heat in nanocluster collisional growth.

ABSTRACT

Nanoclusters can form and grow by nanocluster-monomer collisions (condensation) and nanocluster-nanocluster collisions (coagulation). During growth, product nanoclusters have elevated thermal energies due to potential and thermal energy exchange following a collision. Even though nanocluster collisional heating may be significant and strongly size dependent, no prior theory describes this phenomenon for collisions of finite-size clusters. We derive a model to describe the excess thermal energy of collisional growth, defined as the kinetic energy increase in the product cluster, and latent heat of collisional growth, defined as the heat released to the background upon thermalization of the nonequilibrium cluster. Both quantities are composed of a temperature-independent term related to potential energy minimum differences and a size- and temperature-dependent term, which hinges upon heat capacity and energy partitioning. Example calculations using gold nanoclusters demonstrate that collisional heating can be important and strongly size dependent, particularly for reactive collisions involving nanoclusters composed of 14-20 atoms. Excessive latent heat release may have considerable implications in cluster formation and growth.