Mean-Field Theory of Inhomogeneous Fluids

Abstract

The Barker-Henderson perturbation theory is a bedrock of liquid-state physics, providing quantitative predictions for the bulk thermodynamic properties of realistic model systems. However, this successful method has not been exploited for the study of inhomogeneous systems. We develop and implement a first-principles 'Barker-Henderson density functional', thus providing a robust and quantitatively accurate theory for classical fluids in external fields. Numerical results are presented for the hard-core Yukawa model in three dimensions. Our predictions for the density around a fixed test particle and between planar walls are in very good agreement with simulation data. The density profiles for the free liquid vapour interface show the expected oscillatory decay into the bulk liquid as the temperature is reduced towards the triple point, but with an amplitude much smaller than that predicted by the standard mean-field density functional.

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• Integral equations for simple fluids in a general reference functional approach
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Cited by in corpus (20)

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• Comparative study of force-based classical density functional theory
• Neural density functional theory of liquid-gas phase coexistence
• Long-range interacting systems are locally non-interacting
• The Primitive Model in Classical Density Functional Theory: Beyond the Standard Mean-Field Approximation
• First-principles superadiabatic theory for the dynamics of inhomogeneous fluids
• Local measures of fluctuations in inhomogeneous liquids: Statistical mechanics and illustrative applications
• Structure of liquid--vapor interfaces: perspectives from liquid state theory, large-scale simulations, and potential grazing-incidence X-ray diffraction
• Dynamic Decay and Superadiabatic Forces in the van Hove Dynamics of Bulk Hard Sphere Fluids
• Superadiabatic dynamical density functional study of Brownian hard-spheres in time-dependent external potentials
• Combining integral equation closures with force density functional theory for the study of inhomogeneous fluids
• Superadiabatic dynamical density functional theory for colloidal suspensions under homogeneous steady-shear
• Routes to the density profile and structural inconsistency
• Hard disks confined within a narrow channel