Diffusive Spreading of Chainlike Molecules on Surfaces

We study the diffusion and submonolayer spreading of chainlike molecules on surfaces. Using the fluctuating bond model, we extract the collective and tracer diffusion coefficients Dc and Dₜ with a variety of methods. We show that Dc(θ) has unusual behavior as a function of the coverage θ. It first increases, but after a maximum goes to zero as θ→1. We show that the increase is due to entropic repulsion that leads to steep density profiles for spreading droplets seen in experiments. We also develop an analytic model for Dc(θ) which agrees well with the simulations.