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KH2PO4 (KDP) belongs to the class of hydrogen-bonded ferroelectrics, whoseparaelectric to ferroelectric phase transition is driven by the ordering of theprotons in the hydrogen bonds. We demonstrate that forbidden reflections ofKDP, when measured at an x-ray absorption edge, are highly sensitive to theasymmetry of proton configurations. The change of average symmetry caused bythe "freezing" of the protons during the phase transition is clearly evidenced.In the paraelectric phase, we identify in the resonant spectra of the forbiddenreflections a contribution related to the transient proton configurations inthe hydrogen bonds, which violates the high average symmetry of the sites ofthe resonant atoms. The analysis of the temperature dependence reveals a changeof relative probabilities of the different proton configurations. They followthe Arrhenius law, and the activation energies of polar and Slaterconfigurations are 18.6 and 7.3 meV, respectively.

Proton configurations in the hydrogen bonds of KH2PO4 as seen by resonant x-ray diffraction