Hysteresis, force oscillations, and nonequilibrium effects in the adhesion of spherical nanoparticles to atomically smooth surfaces

Equilibrium and nonequilibrium aspects of particle adsorption on the walls of fluid-filled nanochannels are examined via molecular dynamics simulations. The force on the particle and the free energy of the system are found to depend on the particle's history (hysteresis), in addition to its radial position and the wetting properties of the fluid, even when the particle moves quasistatically. The hysteresis is associated with changes in the fluid density in the gap between the particle and the wall, which persist over surprisingly long times. The force and free energy exhibit large oscillations with distance when the lattice of the structured nanoparticle is held in register with that of the tube wall, but not if the particle is allowed to rotate freely. Adsorbed particles are trapped in free-energy minima in equilibrium but can desorb if forced along the channel.