Long-time molecular diffusion, sedimentation and Taylor dispersion of a fluctuating cluster of interacting Brownian particles

Abstract

Generalized Taylor dispersion theory, incorporating so-called coupling effects, is used to calculate the transport properties of a single deformable ‘chain’ composed of hydrodynamically interacting rigid Brownian particles bound together by internal potentials and moving through an unbounded quiescent viscous fluid. The individual rigid particles comprising the flexible chain or cluster may each be of arbitrary shape, size and density, and are supposed ‘joined’ together to form the chain by a configuration-dependent internal potential V. Each particle separately undergoes translational and rotational Brownian motions; together, their relative motions give rise to a conformational or vibrational Brownian motion of the chain (in addition to a translational motion of the chain as a whole). Sufficient time is allowed for all accessible chain configurations to be sampled many times in consequence of this internal Brownian motion. As a result, an internal equilibrium Boltzmann probabilistic distribution of conformations derived from V effectively obtains.In contrast with prior analyses of such chain transport phenomena, no ad hoc preaveraging hypotheses are invoked to effect the averaging of the input conformation-specific hydrodynamic mobility data. Rather, the calculation is effected rigorously within the usual (quasi-static) context of configuration-specific Stokes-Einstein equations.Explicit numerical calculations serving to illustrate the general scheme are performed only for the simplest case, namely dumb-bells composed of identically sized spheres connected by a slack tether. In this context it is pointed out that prior calculations of flexible-body transport phenomena have failed to explicitly recognize the existence of a Taylor dispersion contribution to the long-time diffusivity of sedimenting deformable bodies. This fluctuation phenomenon is compounded of shape-sedimentation dispersion (arising as a consequence of the intrinsic geometrical anisotropy of the object) and size-sedimentation dispersion (arising from fluctuations in the instantaneous ‘size’ of the object). Whereas shape dispersion exists even for rigid objects, size dispersion is manifested only by flexible bodies. These two Taylor dispersion mechanisms are relevant to interpreting the non-equilibrium sedimentation-diffusion properties of monodisperse polymer molecules in solutions or suspensions.