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In this paper we consider non-compact non-flat simply connected harmonic manifolds. In particular, we show that the Martin boundary and Busemann boundary coincide for such manifolds. For any finite volume quotient we show that (up to scaling) there is a unique Patterson-Sullivan measure and this measure coincides with the harmonic measure. As an application of these results we prove that the geodesic flow on a non-flat finite volume harmonic manifold without conjugate points is topologically transitive.

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