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We show that in mixed-valence 3d transition metal oxides undergoing a structural transition, the low temperature phase results from an effective ordering of the charge. This arrangement and the quantitative evaluation of the atomic charges are determined by using resonant x-ray scattering experiments further analyzed with the help of ab initio calculations of the corresponding scattering factors. We have found that this reorganization concerns only a small fraction of electron and is necessary to reconcile all the experimental data.

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