Negative Hydration Expansion in ZrW2O8: Microscopic Mechanism, Spaghetti Dynamics, and Negative Thermal Expansion

We use a combination of x-ray diffraction, total scattering, and quantum mechanical calculations to determine the mechanism responsible for hydration-driven contraction in ZrW2O8. The inclusion of H2O molecules within the ZrW2O8 network drives the concerted formation of new W-O bonds to give one-dimensional (-W-O-)(n) strings. The topology of the ZrW2O8 network is such that there is no unique choice for the string trajectories: the same local changes in coordination can propagate with a large number of different periodicities. Consequently, ZrW2O8 center dot H2O is heavily disordered, with each configuration of strings forming a dense aperiodic spaghetti. This new connectivity contracts the unit cell via large shifts in the Zr and W atom positions. Fluctuations of the undistorted parent structure towards this spaghetti phase emerge as the key negative thermal expansion (NTE) phonon modes in ZrW2O8 itself. The large relative density of NTE phonon modes in ZrW2O8 actually reflects the degeneracy of volume-contracting spaghetti excitations, itself a function of the particular topology of this remarkable material.