Abstract
The Fokker–Planck (FP) equation describing the dynamics of a single Brownian particle near a fixed external surface is derived using the multiple-time-scales perturbation method, previously used by Cukier and Deutch and Nienhuis in the absence of any external surfaces, and Piasecki et al. for two Brownian spheres in a hard fluid. The FP equation includes an explicit expression for the (time-independent) particle friction tensor in terms of the force autocorrelation function and equilibrium average force on the particle by the surrounding fluid and in the presence of a fixed external surface, such as an adsorbate. The scaling and perturbation analysis given here also shows that the force autocorrelation function must decay rapidly on the zeroth-order time scale τ 0, which physically requires N Kn≪1, where N Kn is the Knudsen number (ratio of the length scale for fluid intermolecular interactions to the Brownian particle length scale). This restricts the theory given here to liquid systems where N Kn≪1. For a specified particle configuration with respect to the external surface, equilibrium canonical molecular dynamics (MD) calculations are conducted, as shown here, in order to obtain numerical values of the friction tensor from the force autocorrelation expression. Molecular dynamics computations of the friction tensor for a single spherical particle in the absence of a fixed external surface are shown to recover Stokes' law for various types of fluid molecule–particle interaction potentials. Analytical studies of the static force correlation function also demonstrate the remarkable principle of force-time parity whereby the particle friction coefficient is nearly independent of the fluid molecule–particle interaction potential. Molecular dynamics computations of the friction tensor for a single spherical particle near a fixed external spherical surface (adsorbate) demonstrate a breakdown in continuum hydrodynamic results at close particle–surface separation distances on the order of several molecular diameters.
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Peters, M.H. Fokker–Planck Equation, Molecular Friction, and Molecular Dynamics for Brownian Particle Transport near External Solid Surfaces. Journal of Statistical Physics 94, 557–586 (1999). https://doi.org/10.1023/A:1004552421971
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DOI: https://doi.org/10.1023/A:1004552421971