Excess entropy determines the applicability of Stokes-Einstein relation in simple fluids

Abstract

The Stokes-Einstein (SE) relation between the self-diffusion and shear viscosity coefficients operates in sufficiently dense liquids not too far from the liquid-solid phase transition. By considering four simple model systems with very different pairwise interaction potentials (Lennard-Jones, Coulomb, Debye-Hückel or screened Coulomb, and the hard sphere limit) we identify where exactly on the respective phase diagrams the SE relation holds. It appears that the reduced excess entropy $s_{\mathrm{ex}}$ can be used as a suitable indicator of the validity of the SE relation. In all cases considered the onset of SE relation validity occurs at approximately $s_{\mathrm{ex}}\lesssim -2$. In addition, we demonstrate that the line separating gas-like and liquid-like fluid behaviours on the phase diagram is roughly characterized by $s_{\mathrm{ex}}\simeq -1$.

arXiv comment12 pages, 5 figures

References in corpus (36)

• Theoretical perspective on the glass transition and amorphous materials
• Mean field theory of hard sphere glasses and jamming
• Two liquid states of matter: A new dynamic line on a phase diagram
• Hard Spheres: Crystallization and Glass Formation
• Anomalous structure and dynamics of the Gaussian-core fluid
• Emergence and evolution of $k$-gap in spectra of liquid and supercritical states
• Generalized Rosenfeld scalings for tracer diffusivities in not-so-simple fluids: Mixtures and soft particles
• Breakdown of The Excess Entropy Scaling for the Systems with Thermodynamic Anomalies
• Structural properties of dense hard sphere packings
• Transport Coefficients of the Yukawa One Component Plasma
• Accurate Determination of the Shear Viscosity of the One-Component Plasma
• Viscosity and mutual diffusion in strongly asymmetric binary ionic mixtures
• Practical expressions for the internal energy and pressure of Yukawa fluids
• Evaluation of phenomenological one-phase criteria for the melting and freezing of softly repulsive particles
• Practical thermodynamics of Yukawa systems at strong coupling
• Practical formula for the shear viscosity of Yukawa fluids
• How to quantify structural anomalies in fluids?
• Internal energy of the classical two- and three-dimensional one-component-plasma
• Self-diffusion in strongly coupled Yukawa systems (complex plasmas)
• Researh Note: Stokes-Einstein relation in simple fluids revisited
• Transport properties of Lennard-Jones fluids: Freezing density scaling along isotherms
• Isomorph-based empirically modified hypernetted-chain approach for strongly coupled Yukawa one-component plasmas
• Effective Coulomb Logarithm for One Component Plasma
• Vibrational model of thermal conduction for fluids with soft interactions
• Practical dispersion relations for strongly coupled plasma fluids
• Simple dispersion relations for Coulomb and Yukawa fluids
• Sound velocities of Lennard-Jones systems near the liquid-solid phase transition
• Classical scattering in strongly attractive potentials
• Two-body entropy of two-dimensional fluids
• Accurate transport cross sections for the Lennard-Jones potential
• When do soft spheres become hard spheres?
• Fast dynamics perspective on the breakdown of the Stokes-Einstein law in fragile glassformers
• Self-diffusion in single-component Yukawa fluids
• Freezing and melting equations for the $n$-6 Lennard-Jones systems
• Note: Sound velocities of generalized Lennard-Jones ($n-6$) fluids near freezing
• Universal Character of Atomic Motions at the Liquid-Solid Transition

Cited by in corpus (18)

• Elementary vibrational model for transport properties of dense fluids
• Minima of shear viscosity and thermal conductivity coefficients of classical fluids
• Freezing density scaling of fluid transport properties: Application to liquefied noble gases
• Sound velocities of Lennard-Jones systems near the liquid-solid phase transition
• Note: Gas-liquid crossover in the Lennard-Jones system
• Excess entropy of strongly coupled Yukawa fluids
• Note: Stokes-Einstein relation without hydrodynamic diameter in the TIP4P/Ice water model
• On the system size dependence of the diffusion coefficients in MD simulations: A simple correction formula for pure dense fluids
• Vibrational model of heat transfer in strongly coupled Yukawa fluids (dusty plasma liquids)
• Freezing density scaling of transport coefficients in the Weeks-Chandler-Andersen fluid
• Elementary vibrational model for thermal conductivity of Lennard-Jones fluids: Applicability domain and accuracy level
• Understanding Dynamics in Coarse-Grained Models: IV. Connection of Fine-Grained and Coarse-Grained Dynamics with the Stokes-Einstein and Stokes-Einstein-Debye Relations
• Quasi-universal behaviour of shear relaxation times in simple fluids
• Generalized Rosenfeld-Tarazona scaling and high-density specific heat of simple liquids
• The Viscosity of Liquids in the Dual Model
• Vibrational model of entropy in dense two-dimensional fluids
• Excess entropy scaling of the transverse sound speed in simple fluids
• Variational approach to Yukawa fluids. II. Instantaneous elastic moduli and sound velocities