By generalising concepts from classical stochastic dynamics, we establish the basis for a theory of metastability in Markovian open quantum systems. Partial relaxation into long-lived metastable states - distinct from the asymptotic stationary state - is a manifestation of a separation of timescales due to a splitting in the spectrum of the generator of the dynamics. We show here how to exploit this spectral structure to obtain a low dimensional approximation to the dynamics in terms of motion in a manifold of metastable states constructed from the low-lying eigenmatrices of the generator. We argue that the metastable manifold is in general composed of disjoint states, noiseless subsystems and decoherence-free subspaces.

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