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Connection between dynamics and thermodynamics of liquids on the melting line

D. Fragiadakis and C. M. Roland

  • Naval Research Laboratory, Chemistry Division, Code 6126, Washington, DC 20375-5342, USA

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Phys. Rev. E 83, 031504 – Published 21 March, 2011

DOI: https://doi.org/10.1103/PhysRevE.83.031504

Abstract

The dynamics of a large number of liquids and polymers exhibit scaling properties characteristic of a simple repulsive inverse power-law potential, most notably the superpositioning of relaxation data as a function of the variable TVγ, where T is temperature, V the specific volume, and γ a material constant. A related scaling law TmVmΓ, with the same exponent Γ=γ, links the melting temperature Tm and volume Vm of the model IPL liquid; liquid dynamics is then invariant at the melting point. Motivated by a similar invariance of dynamics experimentally observed at transitions of liquid crystals, we determine dynamic and melting-point scaling exponents γ and Γ for a large number of nonassociating liquids. Rigid, spherical molecules containing no polar bonds have Γ=γ; consequently, the reduced relaxation time, viscosity, and diffusion coefficient are each constant along the melting line. For other liquids γ > Γ always; that is, the dynamics is more sensitive to volume than is the melting point, and for these liquids the dynamics at the melting point slows down with increasing Tm (that is, increasing pressure).

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Phys. Rev. E 83, 031504– Published 21 March, 2011
  • Received 26 October 2010

©2011 American Physical Society

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