Consequences of minimizing pair correlations in fluids for dynamics, thermodynamics, and structure

Abstract

Liquid-state theory, computer simulation, and numerical optimization are used to investigate the extent to which positional correlations of a hard-sphere fluid--as characterized by the radial distribution function and the two-particle excess entropy--can be suppressed via the introduction of auxiliary pair interactions. The corresponding effects of such interactions on total excess entropy, density fluctuations, and single-particle dynamics are explored. Iso-g processes, whereby hard-sphere-fluid pair structure at a given density is preserved at higher densities via the introduction of a density-dependent, soft repulsive contribution to the pair potential, are considered. Such processes eventually terminate at a singular density, resulting in a state that--while incompressible and hyperuniform--remains unjammed and exhibits fluid-like dynamic properties. The extent to which static pair correlations can be suppressed to maximize pair disorder in a fluid with hard cores, determined via direct functional maximization of two-body excess entropy, is also considered. Systems approaching a state of maximized two-body entropy display a progressively growing bandwidth of suppressed density fluctuations, pointing to a relation between "stealthiness" and maximal pair disorder in materials.

12 pages, 8 figures

References in corpus (26)

• Jamming at Zero Temperature and Zero Applied Stress: the Epitome of Disorder
• Is Random Close Packing of Spheres Well Defined?
• Jammed Hard-Particle Packings: From Kepler to Bernal and Beyond
• Local Density Fluctuations, Hyperuniformity, and Order Metrics
• Mean field theory of hard sphere glasses and jamming
• Pair Correlation Function Characteristics of Nearly Jammed Disordered and Ordered Hard-Sphere Packings
• Unexpected Density Fluctuations in Jammed Disordered Sphere Packings
• Crystallization of hard-sphere glasses
• Why is Random Close Packing Reproducible?
• Classical Disordered Ground States: Super-Ideal Gases, and Stealth and Equi-Luminous Materials
• Thermodynamics predicts how confinement modifies hard-sphere dynamics
• A theory of amorphous packings of binary mixtures of hard spheres
• Anomalous structure and dynamics of the Gaussian-core fluid
• Generalized Rosenfeld scalings for tracer diffusivities in not-so-simple fluids: Mixtures and soft particles
• Experimental study of random close packed colloidal particles
• Perspective: Inverse methods for material design
• Tuning density profiles and mobility of inhomogeneous fluids
• Generalizing Rosenfeld's excess-entropy scaling to predict long-time diffusivity in dense fluids of Brownian particles: From hard to ultrasoft interactions
• Structural anomalies of fluids: Origins in second and higher coordination shells
• Estimates of the optimal density and kissing number of sphere packings in high dimensions
• Universal Jamming Phase Diagram in the Hard-Sphere Limit
• Composition and concentration anomalies for structure and dynamics of Gaussian-core mixtures
• Equilibrium equation of state of a hard sphere binary mixture at very large densities using replica exchange Monte-Carlo simulations
• Molecular dynamics of a dense fluid of polydisperse hard spheres
• Enhancing tracer diffusivity by tuning interparticle interactions and coordination shell structure
• Tuning structure and mobility of solvation shells surrounding tracer additives