Effect of crowding and confinement on first-passage times: A model study

We study the "color dynamics" of a hard-disk fluid confined in an annulus, as well as the corresponding hard-sphere system in three dimensions, using event-driven simulation in order to explore the effect of confinement and self-crowding on the search for targets. We compute the mean first-passage times (MFPTs) of red particles transiting from the outer to the inner boundary as well as those of blue particles passing from the inner to the outer boundary for different packing fractions and geometries. In the steady state the reaction rate, defined as the rate of collision of red particles with the inner boundary, is inversely proportional to the sum of the MFPTs. The reaction rate is wall mediated (ballistic) at low densities and diffusion controlled at higher densities and displays a maximum at intermediate densities. At moderate to high densities, the presence of layering has a strong influence on the search process. The numerical results for the reaction rate and MFPTs are compared with a ballistic model at low densities and a Smoluchowski approach with uniform diffusivities at higher densities. We discuss the reasons for the limited validity of the theoretical approaches. The maximum in the reaction rate is qualitatively well rendered by a Bosanquet-like approach that interpolates between the two regimes. Finally, we compute the position-dependent diffusivity from the MFPTs and observe that it is out of phase with the radial density.