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A set of X-ray diffraction data on the crystal-lattice transformations of the α-Cu2V2O7 phase demonstrates that, in regions with an anomalous negative and near-zero volumetric thermal expansion, both vanadium‒oxygen and copper‒oxygen sublattices are maximally deformed. The near-zero and negative volumetric thermal expansion of the α-Cu2V2O7 unit cell arises from the degeneration of zigzag copper‒oxygen...
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