,Fractional Stokes-Einstein relation in TIP5P water at high temperatures

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Fractional Stokes-Einstein relation described by D ~ (τ/T)ξ is observed in supercooled water,where D is the diffusion constant,τ the structural relaxation time,T the temperature,and the exponent ξ ~-1.In this work,the StokesEinstein relation in TIP5P water is examined at high temperatures within 400 K-800 K.Our results indicate that the fractional Stokes-Einstein relation is explicitly existent in TIP5P water at high temperatures,demonstrated by the two usually adopted variants of the Stokes-Einstein relation,D ~ τ-1and D ~ T/τ,as well as by D ~ T/rη,where ηis the shear viscosity.Both D ~ τ-1 and D ~ T/τ are crossed at temperature Tx =510 K.The D ~ τ-1 is in a fractional form as D ~ τξ with ξ =-2.09 for T ≤ Tx and otherwise ξ =-1.25.The D ~ T/τ is valid with ξ =-1.01 for T ≤ Tx but in a fractional form for T > Tx.The Stokes-Einstein relation D ~ T/η is satisfied below Tx =620 K but in a fractional form above Tx.We propose that the breakdown of D ~ T/η may result from the system entering into the super critical region,the fractional forms of D ~ τ-1 and D ~ T/τ are due to the disruption of the hydration shell and the local tetrahedral structure as well as the increase of the shear viscosity.
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