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In this paper we present a novel approach to the problem of speaker segmentation, which is an unavoidable previous step to audio indexing. Mutual information is used for evaluating the accuracy of the segmentation, as a function to be maximized by a simulated annealing (SA) algorithm. We introduce a novel mutation operator for the SA, the Consecutive Bits Mutation operator, which improves the performance of the SA in this problem. We also use the so-called Compaction Factor, which allows the SA to operate in a reduced search space. Our algorithm has been tested in the segmentation of real audio databases, and it has been compared to several existing algorithms for speaker segmentation, obtaining very good results in the test problems considered.