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Matrix product vectors form the appropriate framework to study and classify one-dimensional quantum systems. In this work, we develop the structure theory of matrix product unitary operators (MPUs) which appear e.g. in the description of time evolutions of one-dimensional systems. We prove that all MPUs have a strict causal cone, making them quantum cellular automata (QCAs), and derive a canonical form for MPUs which relates different MPU representations of the same unitary through a local gauge. We use this canonical form to prove an index theorem for MPUs which gives the precise conditions under which two MPUs are adiabatically connected, providing an alternative derivation to that of (Gross et al 2012 Commun. Math. Phys. 310 419) for QCAs. We also discuss the effect of symmetries on the MPU classification. In particular, we characterize the tensors corresponding to MPU that are invariant under conjugation, time reversal, or transposition. In the first case, we give a full characterization of all equivalence classes. Finally, we give several examples of MPU possessing different symmetries., Unión Europea. H2020, Ministerio de Economía y Competitividad (MINECO), ICMAT Severo Ochoa, Comunidad de Madrid, Depto. de Análisis Matemático y Matemática Aplicada, Fac. de Ciencias Matemáticas, TRUE, pub