NORMAL MODE THEORY FOR THE BROWNIAN DYNAMICS OF A WEAKLY BENDING ROD - COMPARISON WITH BROWNIAN DYNAMICS SIMULATIONS

A normal mode theory is developed for the Brownian dynamics of weakly bending rods with preset hydrodynamic interactions. The rod is replaced by a chain of contiguous spheres whose radius is chosen to yield the appropriate uniform translational and rotational diffusion coefficients. Despite the inclusion of preset hydrodynamic interactions in the dynamical operator, its normal modes are not coupled by the potential energy, so their amplitudes remain pairwise “orthogonal” under equilibrium averaging. The uniform translational and rotational diffusion coefficients obtained from Langevin theory are shown to be identical to those obtained from the Kirkwood algorithm, despite their rather different appearance. An expression is given for the mean squared angular displacement 〈Δxm(t)2〉 of the mth bond vector around the instantaneous x axis (perpendicular to the end‐to‐end vector z). Necessary algorithms are presented for the numerical evaluation of all quantities. The normal mode theory is compared with Brownian dynamics simulations for the same model by examining 3〈Δxm(t)2〉 for the central bond vector of rods comprising 10 and 30 subunits with various persistence lengths. The normal mode theory works very well for all times for L/P ≲ 0.6, where P = κ/kBT is the persistence length and κ is the bending rigidity. With increasing flexibility, the domain of validity of the normal mode theory is restricted to shorter times, where violations of the weak bending approximation are less severe. However, increasing the length of the rod from 10 to 30 subunits yields improved agreement with the simulations for the same and even longer times. This latter effect is tentatively attributed to the greater fluctuating tension in the longer chains, which acts to retard the rotational relaxation in the simulations, but is not taken into account in the present normal mode theory. Copyright © 1990 John Wiley & Sons, Inc.