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Diffusion of hard disks and rodlike molecules on surfaces

机译:硬盘和棒状分子在表面的扩散

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摘要

We study the submonolayer diffusion of hard disks and rodlike molecules on smooth surfaces through numerical simulations and theoretical arguments. We concentrate on the behavior of the various diffusion coefficients as a function of the two-dimensional (2D) number density ρ in the case where there are no explicit surface-particle interactions. For the hard disk case, we find that while the tracer diffusion coefficient DT(ρ) decreases monotonically up to the freezing transition, the collective diffusion coefficient DC(ρ) is wholly determined by the inverse compressibility which increases rapidly on approaching freezing. We also study memory effects associated with tracer diffusion, and present theoretical estimates of DT(ρ) from the mode-mode coupling approximation. In the case of rigid rods with short-range repulsion and no orientational ordering, we find behavior very similar to the case of disks with the same repulsive interaction. Both DT(ρ) and the angular diffusion coefficient DR(ρ) decrease with ρ. Also in this case DC(ρ) is determined by inverse compressibility and increases rapidly close to freezing. This is in contrast to the case of flexible chainlike molecules in the lattice-gas limit, where DC(ρ) first increases and then decreases as a function of the density due to the interplay between compressibility and mobility.
机译:我们通过数值模拟和理论论证研究了硬盘和棒状分子在光滑表面上的亚单层扩散。在没有明确的表面-粒子相互作用的情况下,我们着眼于各种扩散系数的行为,该行为是二维(2D)数密度ρ的函数。对于硬盘情况,我们发现,示踪剂扩散系数DT(ρ)在冻结转变之前单调降低,而总扩散系数DC(ρ)则完全由逆压缩率决定,反压缩率在接近冻结时迅速增加。我们还研究了与示踪剂扩散相关的记忆效应,并从模式-模式耦合近似中给出了DT(ρ)的理论估计。对于具有短程推斥力且没有方向有序性的刚性杆,我们发现其行为与具有相同推斥作用的圆盘情况非常相似。 DT(ρ)和角扩散系数DR(ρ)都随ρ减小。同样在这种情况下,DC(ρ)由逆压缩性确定,并在接近冻结时迅速增加。这与晶格气体极限中的柔性链状分子的情况相反,在这种情况下,由于可压缩性和迁移率之间的相互作用,DC(ρ)首先根据密度增加然后减小。

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