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We study the coverage dependence of surface diffusion for chainlike molecules by the fluctuating-bond model with a Monte Carlo dynamics. The model includes short-ranged excluded volume interactions between different chains as well as an intrachain bond angle potential to describe the chain stiffness. Our primary aim is to consider the role played by chain stiffness and the resulting memory effects in tracer diffusion, and in particular their role in the effective tracer diffusion barrier EAT extracted from the well-known Arrhenius form. We show that the memory effects in tracer diffusion become more pronounced at an increasing coverage as a result of packing requirements. Increasing the chain flexibility furthermore has the same overall effect as increasing the chain length, namely, they both increase EAT. We then analyze the influence of memory effects on EAT and find that, for a single diffusing chain, about 20% of EAT arises from temperature variations in the memory effects, while only the remaining pa...

Surface diffusion of long chainlike molecules: The role of memory effects and stiffness on effective diffusion barriers