Understanding and Controlling Regime Switching in Molecular Diffusion

Abstract

Diffusion can be strongly affected by ballistic flights (long jumps) as well as long-lived sticking trajectories (long sticks). Using statistical inference techniques in the spirit of Granger causality, we investigate the appearance of long jumps and sticks in molecular-dynamics simulations of diffusion in a prototype system, a benzene molecule on a graphite substrate. We find that specific fluctuations in certain, but not all, internal degrees of freedom of the molecule can be linked to either long jumps or sticks. Furthermore, by changing the prevalence of these predictors with an outside influence, the diffusion of the molecule can be controlled. The approach presented in this proof of concept study is very generic, and can be applied to larger and more complex molecules. Additionally, the predictor variables can be chosen in a general way so as to be accessible in experiments, making the method feasible for control of diffusion in applications. Our results also demonstrate that data-mining techniques can be used to investigate the phase-space structure of high-dimensional nonlinear dynamical systems.

accepted for publication by PRE

References in corpus (6)

• Power-law distributions in empirical data
• Powerlaw: a Python package for analysis of heavy-tailed distributions
• Atomic scale friction of molecular adsorbates during diffusion
• Measuring logarithmic corrections to normal diffusion in infinite-horizon billiards
• Internal degrees of freedom and transport of benzene on graphite
• Relating chaos to deterministic diffusion of a molecule adsorbed on a surface

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