We consider a diffusion given by a small noise perturbation of a dynamical system driven by a potential function with a finite number of local minima. The classical results of Freidlin and Wentzell show that the time this diffusion spends in the domain of attraction of one of these local minima is approximately exponentially distributed and hence the diffusion should behave approximately like a Markov chain on the local minima. By the work of Bovier and collaborators, the local minima can be associated with the small eigenvalues of the diffusion generator. Applying a Markov mapping theorem, we use the eigenfunctions of the generator to couple this diffusion to a Markov chain whose generator has eigenvalues equal to the eigenvalues of the diffusion generator that are associated with the local minima and establish explicit formulas for conditional probabilities associated with this coupling. The fundamental question then becomes to relate the coupled Markov chain to the approximate Markov chain suggested by the results of Freidlin and Wentzel. We provide a complete analysis of this relationship in the special case of a double-well potential in one dimension. More generally, the coupling can be constructed for a general class of Markov processes and any finite set of eigenvalues of the generator.