High-resolution neutron-scattering study of slow dynamics of surface water molecules in zirconium oxide.
We have performed a quasielastic neutron-scattering experiment on backscattering spectrometer with sub-mueV resolution to investigate the slow dynamics of surface water in zirconium oxide using the sample studied previously with a time-of-flight neutron spectrometer [E. Mamontov, J. Chem. Phys. 121, 9087 (2004)]. The backscattering measurements in the temperature range of 240-300 K have revealed a translational dynamics slower by another order of magnitude compared to the translational dynamics of the outer hydration layer observed in the time-of-flight experiment. The relaxation function of this slow motion is described by a stretched exponential with the stretch factors between 0.8 and 0.9, indicating a distribution of the relaxation times. The temperature dependence of the average residence time is non-Arrhenius, suggesting that the translational motion studied in this work is more complex than surface jump diffusion previously observed for the molecules of the outer hydration layer. The observed slow dynamics is ascribed to the molecules of the inner hydration layer that form more hydrogen bonds compared to the molecules of the outer hydration layer. Despite being slower by two orders of magnitude, the translational motion of the molecules of the inner hydration layer may have more in common with bulk water compared to the outer hydration layer, the dynamics of which is slower than that of bulk water by just one order of magnitude.
Mamontov
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National Institute of Standards and Technology (NIST) Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8562, USA. mamontov@nist.gov
D002627:Chemistry, Physical / Q000379:methods; D006860:Hydrogen Bonding; D015233:Models, Statistical; D033363:Neutron Diffraction; D009502:Neutrons; D012542:Scattering, Radiation; D013053:Spectrophotometry / Q000379:methods; D013499:Surface Properties; D013696:Temperature; D013997:Time Factors; D014867:Water / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry*
D014867:Water; D015040:Zirconium; C028541:zirconium oxide