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The Ti dopant occupying Li or Nb sites and the charge transfer processes induced by thermochemical reduction and optical bleaching treatments have been investigated in LiNbO3 systems using optical absorption and EPR. The Ti3+ centers, built preferentially at Nb sites in heavily Mg-codoped crystals, are shown to have absorption bands at 1.620.08eV and 2.650.25eV, which are similar or slightly redshifted...