On the validity of stochastic rate equations in finite systems with finite-strength interactions

Starting with the Hamiltonian for a linear harmonic chain of 2N particles of massm and one of massM, we have carried out numerical calculations for the momentum autocorrelation function of the mass defect particle for chains with finite numberN of mass points and for nonzero values of the mass ratio=m/M. These results have been compared with the well-known exponential relaxation of the momentum autocorrelation function which is found to be the rigorous result when passing to the thermodynamic and weak-coupling limit. In these limits, the dynamics of the mass defect particle is exactly described by a Fokker-Planck equation, i.e., a stochastic equation of motion. We have shown that, to an excellent approximation, an exponential relaxation of the momentum autocorrelation function is obtained for mass ratios as high as=0.1 and for chains with only 50 particles. Thus, for the harmonic chain considered here, the stochastic equations of motion can be applied to a very good approximation far outside the usually imposed thermodynamic and weak-coupling limits.Supported in part by the Advanced Research Projects Agency of the Department of Defense as monitored by the U.S. Office of Naval Research under Contract N00014-69-A-0200-6018 and by the National Science Foundation under Grant GP28257X.