Metastability in Markov processes

We present a formalism for describing slowly decaying systems in the context of finite Markov chains obeying detailed balance. We show that phase space can be partitioned into approximately decoupled regions, in which one may introduce restricted Markov chains which are close to the original process but do not leave these regions. Within this context, we identify the conditions under which the decaying system can be considered to be in a metastable state. Furthermore, we show that such metastable states can be described in thermodynamic terms and de. ne their free energy. This is accomplished, showing that the probability distribution describing the metastable state is indeed proportional to the equilibrium distribution, as is commonly assumed. We test the formalism numerically in the case of the two-dimensional kinetic Ising model, using the Wang-Landau algorithm to show this proportionality explicitly, and confirm that the proportionality constant is as derived in the theory. Finally, we extend the formalism to situations in which a system can have several metastable states.