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Area of Science:

  • Thermodynamics
  • Fluid Dynamics
  • Statistical Mechanics

Background:

  • Distinguishing between gas-like and liquid-like behaviors in fluids is crucial for understanding phase transitions and transport properties.
  • Existing frameworks often treat structural and dynamic aspects separately, leading to complex definitions of fluid state crossovers.

Purpose of the Study:

  • To propose a simple, generic definition for the gas-liquid crossover line.
  • To reconcile structural and dynamic frameworks using an entropy scaling approach.
  • To establish a link between fluid transport properties and local structure.

Main Methods:

  • Defined the crossover line based on the equality of individual (translational viscosity) and collective (interaction viscosity) contributions.
  • Validated the definition against minima in kinematic viscosity.
  • Tested the definition for hard spheres, Lennard-Jones spheres and dimers, and simple real fluids.
  • Compared the crossover line with the critical excess entropy curve for atomic fluids.

Main Results:

  • A novel, generic definition of the gas-liquid crossover line was proposed and validated.
  • The definition showed consistency with kinematic viscosity minima for various fluid models.
  • The crossover line was found to pass near the critical point for studied fluids.
  • The critical excess entropy curve accurately captured the crossover line for atomic fluids.

Conclusions:

  • The proposed definition provides a unified approach to characterizing fluid behavior.
  • The study highlights a strong connection between transport properties (viscosity) and local fluid structure.
  • The findings offer insights into the fundamental nature of phase transitions and fluid dynamics.