Raman scattering in detwinned YBa 2 Cu 3 O 6.65 single crystals is studied as a function of photoexcitation and annealing. Copper-oxygen chain-related forbidden Raman bands that are known to strongly bleach with illumination at low temperatures, increase their intensity with chain fragmentation induced by annealing at high temperature. This contrasting behavior proves the conjunction of short Cu-O fragments into longer chains on photoexcitation. We interpret the Raman modes as due to vibrations

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... at the end of CuO chain fragments and Cu-O-Cu monomers, and use their evolution with illumination and annealing as anisotropic sensitive markers of oxygen reordering processes. The identification of the "forbidden" Raman bands is discussed in the context of our results and recent literature in the subject. We also present absorption measurements performed on GdBa 2 Cu 3 O x thin films with varying oxygen content. These experiments show that the 2.2-eV absorption and the chain-related Raman peaks have different dependencies with oxygen content and illumination, ruling out an explanation that suggests that the Raman intensity reduction of these modes is due to a photobleaching of intermediate defect states. These results highlight the potentialities of Raman scattering for oxygen dynamics studies and demonstrate the presence of photoinduced oxygen ordering in these high-T c superconductor compounds.