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The method can be used as a general purpose optimization technique to locate the minima of an arbitrary function defined on a finite but possibly very large set. It can be described as a non-stationary controlled Markov chain. The aim of this paper is to build a large deviation theory in this time-inhomogeneous discrete setting. A careful investigation of the law of the exit point and time from sets is made, based on the Venttsel'-Frejdlin decomposition of the state space into cycles. It is hoped that giving a precise description of how trajectories escape from attractors brings a qualitative contribution to the insight one may have into the behaviour of simulated annealing. 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