Dynamics of Chainlike Molecules on Surfaces

We consider the diffusion and spreading of chainlike molecules on solid surfaces. We first show that the steep spherical cap shape density profiles, observed in some submonolayer experiments on spreading polymer films, imply that the collective diffusion coefficient $D_C(\theta)$ must be an increasing function of the surface coverage $\theta$ for small and intermediate coverages. Through simulations of a discrete model of interacting chainlike molecules, we demonstrate that this is caused by an entropy-induced repulsive interaction. Excellent agreement is found between experimental and numerically obtained density profiles in this case, demonstrating that steep submonolayer film edges naturally arise due to the diffusive properties of chainlike molecules. When the entropic repulsion dominates over interchain attractions, $D_C(\theta)$ first increases as a function of $\theta$ but then eventually approaches zero for $\theta \to 1$. The maximum value of $D_C(\theta)$ decreases for increasing attractive interactions, leading to density profiles that are in between spherical cap and Gaussian shapes. We also develop an analytic mean field approach to explain the diffusive behavior of chainlike molecules. The thermodynamic factor in $D_C(\theta)$ is evaluated using effective free energy arguments, and the chain mobility is calculated numerically using the recently developed dynamic mean field theory. Good agreement is obtained between theory and simulations.Comment: 16 pages, 13 Postscript figure

Nonexponential decay of velocity correlations in surface diffusion: The role of interactions and ordering

We study the diffusive dynamics of adparticles in two model systems with strong interactions by considering the decay of the single-particle velocity correlation function φ(t). In accordance with previous studies, we find φ(t) to decay nonexponentially and follow a power-law φ(t)∼t−x at intermediate times t, while at long times there is a crossover to an exponential decay. We characterize the behavior of the decay exponent x in detail in various ordered phases and in the vicinity of phase boundaries. We find that within the disordered phase, the behavior of x can be rationalized in terms of interaction effects. Namely, x is typically larger than two in cases where repulsive adparticle–adparticle interactions dominate, while attractive interactions lead to x<2. In ordered phases, our results suggest that the behavior of x is mainly governed by ordering effects that determine the local structure in which adatoms diffuse. Then the decay is characterized by 1<x<2 under conditions where diffusion is truly two-dimensional, while in phases where adatoms diffuse in a one-dimensional fashion along ideal rows of vacancies, we find a regime characterized by x<1. Also, changes in the qualitative behavior of x are closely related to phase boundaries and local ordering effects. Our studies suggest that φ(t) can be used to obtain information about the ordering of the system and about the nature of predominant interactions between adparticles. Our predictions can be tested experimentally by techniques such as scanning tunneling microscopy, in which φ(t) can be measured in terms of discrete adparticle displacements as shown in this work. Finally, our studies suggest that the decay of velocity correlations in collective diffusion follows, qualitatively, the same behavior as the decay of single-particle velocity correlations in tracer diffusion.Peer reviewe

Diffusion of hard disks and rodlike molecules on surfaces

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.Peer reviewe

Memory expansion for diffusion coefficients

We present a memory expansion for macroscopic transport coefficients such as the collective and tracer diffusion coefficients DC and DT, respectively. The successive terms in this expansion for DC describe rapidly decaying memory effects of the center-of-mass motion, leading to fast convergence when evaluated numerically. For DT, one obtains an expansion of similar form that contains terms describing memory effects in single-particle motion. As an example we evaluate DC and DT for three strongly interacting surface systems through Monte Carlo simulations, and for a simple model diffusion system via molecular dynamics calculations. We show that the numerical method provides a speedup of about two orders of magnitude in computational time as compared with the standard methods, when collective diffusion is concerned. For tracer diffusion, the speedup is not quite as significant. Our studies using the memory expansion provide information of the nature of memory effects in diffusion and suggest a nontrivial power-law behavior of memory terms at intermediate times. We also discuss the application of the present approach to studies of other transport coefficients.Peer reviewe

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 D_c and D_t with a variety of methods. We show that D_c(theta) has unusual behavior as a function of the coverage theta. It first increases but after a maximum goes to zero as theta go to one. 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 D_c(theta) which agrees well with the simulations.Comment: 3 pages, RevTeX, 4 postscript figures, to appear in Phys. Rev. Letters (1996

A Dynamical Mean Field Theory for the Study of Surface Diffusion Constants

We present a combined analytical and numerical approach based on the Mori projection operator formalism and Monte Carlo simulations to study surface diffusion within the lattice-gas model. In the present theory, the average jump rate and the susceptibility factor appearing are evaluated through Monte Carlo simulations, while the memory functions are approximated by the known results for a Langmuir gas model. This leads to a dynamical mean field theory (DMF) for collective diffusion, while approximate correlation effects beyond DMF are included for tracer diffusion. We apply our formalism to three very different strongly interacting systems and compare the results of the new approach with those of usual Monte Carlo simulations. We find that the combined approach works very well for collective diffusion, whereas for tracer diffusion the influence of interactions on the memory effects is more prominent.Comment: 13 pages LaTeX and 6 PostScript figures, style files included. To appear in Surface Science Letter

Non-Arrhenius Behavior of Surface Diffusion Near a Phase Transition Boundary

We study the non-Arrhenius behavior of surface diffusion near the second-order phase transition boundary of an adsorbate layer. In contrast to expectations based on macroscopic thermodynamic effects, we show that this behavior can be related to the average microscopic jump rate which in turn is determined by the waiting-time distribution W(t) of single-particle jumps at short times. At long times, W(t) yields a barrier that corresponds to the rate-limiting step in diffusion. The microscopic information in W(t) should be accessible by STM measurements.Comment: 4 pages, Latex with RevTeX macro

Dynamics and Scaling of 2D Polymers in a Dilute Solution

The breakdown of dynamical scaling for a dilute polymer solution in 2D has been suggested by Shannon and Choy [Phys. Rev. Lett. {\bf 79}, 1455 (1997)]. However, we show here both numerically and analytically that dynamical scaling holds when the finite-size dependence of the relevant dynamical quantities is properly taken into account. We carry out large-scale simulations in 2D for a polymer chain in a good solvent with full hydrodynamic interactions to verify dynamical scaling. This is achieved by novel mesoscopic simulation techniques