The approach to hard-sphere brownian motion: Variational eigenfunctions and evaluation of the Rayleigh-Fokker-Planck equation

Abstract

We present detailed tabulations of the first few eigenfunctions of the hard-sphere energy scattering kernel for a test-particle in a background heat-bath. Calculations, for a range of heat bath/test particle mass-ratios between 1 8 and 1 1024 , were carried out by a Rayleigh-Ritz method using the exact solutions of the hard-sphere Fokker-Planck equation as a basis set and supplement our previously-published results for the eigenvalues alone. The results, given as expansion coefficients in this representation thus also serve to verify the accuracy of the Fokker-Planck equation itself, the departure from this equation being reflected in the off-diagonal contributions in the Rayleigh-Ritz expansion eigenvectors. As expected, the tendency towards brownian motion behaviour with decrease in the mass-ratio parameter shows itself in a progressive convergence of a larger and larger subset of the true eigenfunctions to the corresponding Fokker-Planck set, beginning with the eigenvalue of lowest index. The class of probability distributions whose evolution is satisfactory predicted by the Fokker-Planck equation is then precisely the class that can be adequately expanded in terms of this incomplete subset. In keeping with the approximations introduced in the derivation of the Fokker-Planck equation and the qualitative nature of the hard-sphere eigenvalue spectrum, the results confirm quantitatively the considerable restrictions which the former imposes upon acceptable solution functions, excluding in particular both short-time behaviour and solutions of insufficient smoothness. A mean-square criterion for accuracy of the Fokker-Planck solutions is suggested and examined in the light of our numerical results.