Simulations of aerosol aggregation including long-range interactions

Current understanding of solid aerosol particle aggregation is limited to simulation models based on diffusive and ballistic motion of the colliding particles. The role of the long-range van der Waals forces in aggregation phenomena, although important, has never been examined. In an effort to address this issue, a simulation model, based on molecular dynamics techniques, is developed. Using this model to simulate thermal collisions of single spheres with small aggregates of similar spheres, we examine the effects of retardation of the long-range van der Waals forces, particle transport, ambient temperature, and pressure on the collision rates and mass and structure distributions of the aggregated particles. The model calculations were performed at simulated temperatures of 293 and 1500 K and at simulated pressures of 760 and 3040 torr for glassy carbon primary particles in the free molecular regime with diameters of 6 nm, and in the transition regime with diameters of 30 nm. Inclusion of the long-range van der Waals forces resulted in aggregates with relatively open structures and few branches and collision rate constants that were larger than the corresponding hard sphere rate constants, whereas exclusion of the forces resulted in compact structures with more branches and smaller enhancements in the rate constants. The above effects were found to be more pronounced in the free molecular regime than in the transition regime, which is consistent with the observation that the initial conditions and the interparticle forces play a more significant role in particle transport in the free molecular regime than in the transition regime. The effect of retardation of the forces is an increase in the percentage of open aggregates and the collision rate constants over that of the corresponding nonretarded case. An increase in temperature resulted in a collapse of aggregate structure and a decrease in collision rate constants corresponding to the reduced geometrical cross sections. Again, the effects were found to be more pronounced in the free molecular regime than in the transition regime. No significant difference was observed in the structure of the aggregates or in the collision rate constants with a change in pressure, indicating that the pressure effect, if any, is hidden by the much stronger effect of the long-range van der Waals forces.