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We present the first experimental analysis of the chlorinewater distribution in the glassy and liquid state of LiCl.6D20. The results are based on neutron diffraction experiments performed at aspallation source. Evidence ofa fundamental structural change within the hydration shell around a chlorine ion in the glassy state is given although the D 2 0 intramolecular characteristics remain unchanged, At the same time, as the water molecules become more localized within the chlorine hydration shell, the system orders over nearly twice the distance (three moreD,Oshells beinEdetectable) and this is possiblyaccompanied by an ordering of the ion distribution