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Communications: The fractional Stokes–Einstein equation: Application to water
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Previously [K. R. Harris, J. Chem. Phys.131, 054503 (2009)] it was shown that both real and model liquids fit the fractional form of the Stokes–Einstein relation [fractional Stokes–Einstein (FSE)] over extended ranges of temperature and density. For example, the self-diffusion coefficient and viscosity of the Lennard-Jones fluid fit the relation with and a range of molecular and ionic liquids for which high pressure data are available behave similarly, with values between 0.79 and 1. At atmospheric pressure, normal and heavy water were also found to fit FSE from 238 to 363 K and from 242 to 328 K, respectively, but with distinct transitions in the supercooled region at about 258 and 265 K, respectively, from (high temperature) to 0.67 (low temperature). Here the recent self-diffusion data of Yoshida et al. [J. Chem. Phys.129, 214501 (2008)] for the saturation line are used to extend the high temperature fit to FSE to 623 K for both isotopomers. The FSE transition temperature in bulk water can be contrasted with much lower values reported in the literature for confined water.
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