Exact analytic solution for the correlation time of a Brownian particle in a double-well potential from the Langevin equation

The correlation time of the positional autocorrelation function is calculated exactly for one-dimensional translational Brownian motion of a particle in a 2-4 double-well potential in the noninertial limit. The calculations are carried out using the method of direct conversion (by averaging) of the Langevin equation for a nonlinear stochastic system to a set of differential-recurrence relations. These, in the present problem, reduce on taking the Laplace transform, to a three-term recurrence relation. Thus the correlation time T-c of the positional autocorrelation function may be formally expressed as a sum of products of infinite continued fractions which may be represented in series form as a sum of two term products of Whittaker's parabolic cylinder functions. The sum of this series may be expressed as an integral using the integral representation of the parabolic cylinder functions and subsequently the Taylor expansion of the error function, thus yielding the exact solution for T-c. This solution is in numerical agreement with that obtained by Perico et al. [J. Chem. Phys. 98, 564 (1993)] using the first passage time approach while previous asymptotic results obtained by solving the underlying Smoluchowski equation an recovered in the limit of high barrier heights. A simple empirical formula which provides a close approximation to the exact solution for all barrier heights is also given. (C) 1996 American Institute of Physics.