A molecular-dynamics simulation study of the adsorption and diffusion dynamics of short n-alkanes on Pt(111)

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Abstract
Using molecular‐dynamics studies and static potential‐energy minimization, we have resolved the mechanisms by which n‐alkanes (ethane through n‐decane) diffuse on a model Pt(111) surface in the low‐coverage limit of a single adsorbed molecule. Our simulations reproduce all of the experimental trends seen for the adsorption and diffusion of C3–C6 on Pt(111) and Ru(001). The short alkanes (C2–C8) behave as rigid rods and their motion involves coupled translation and rotation in the surface plane. For this series, there is a linear increase of the diffusion barrier with the molecular chain length. We have analyzed the compliance of the motion of the assumptions of a nearest‐neighbor hopping model. Although hopping motion can be observed for all of the molecules at sufficiently low temperatures, the hopping involves a significant fraction of long jumps. As the temperature increases, the adsorption becomes virtually delocalized. Despite the extensive deviations of the motion from the assumptions of a nearest‐neighbor hopping model, the static diffusion‐energy barriers, arising from the minimum‐energy path for hops between nearest‐neighbor binding sites, agree well with those obtained from the tracer‐diffusion coefficients for butane, hexane, and octane. For these molecules, multiple‐site hops and long flights appear to influence the values of the preexponential factors, which are too large. Neither the diffusion barrier nor the preexponential factor for ethane agrees well with theoretical estimates. We attribute these discrepancies to the smallness of the static diffusion barrier and/or the existence of unique dynamical behavior for this molecule. Due to the increased difficulty of in‐plane rotation and increased mismatch between the geometries of the molecule and the surface, the diffusion barrier for n‐decane drops below that for n‐hexane. The characteristic mechanism of motion for n‐decane involves significant C–C–C bond‐angle bending.