Journal of Chemical Physics, Vol.113, No.1, 258-265, 2000
Rayleigh-Ritz calculation of the activation rate in the spatial diffusion regime
We propose a Rayleigh-quotient-based perturbation method for estimating the least nonvanishing eigenvalue of the Fokker-Planck equation in the spatial diffusion regime. Comparison of the resulting expression against exact numerical rates in a symmetric double well produces excellent agreement at all barrier heights. The corresponding relative error is lower by more than an order of magnitude than those of existing finite-barrier expansions.