Microscopic Theory for the Role of Attractive Forces in the Dynamics of Supercooled Liquids

Abstract

We formulate a microscopic, no adjustable parameter, theory of activated relaxation in supercooled liquids directly in terms of the repulsive and attractive forces within the framework of pair correlations. Under isochoric conditions, attractive forces can nonperturbatively modify slow dynamics, but at high enough density their influence vanishes. Under isobaric conditions, attractive forces play a minor role. High temperature apparent Arrhenius behavior and density-temperature scaling are predicted. Our results are consistent with recent isochoric simulations and isobaric experiments on a deeply supercooled molecular liquid. The approach can be generalized to treat colloidal gelation and glass melting, and other soft matter slow dynamics problems.

arXiv commentAccepted to Physical Review Letters. Main Text: 6 pages, 4 figures. Supplementary Materials (appended at end of file): 6 pages, 4 figures

References in corpus (19)

• Theoretical perspective on the glass transition and amorphous materials
• Supercooled Liquids for Pedestrians
• Colloidal Gels: Equilibrium and Non-Equilibrium Routes
• Nonergodicity transitions in colloidal suspensions with attractive interactions
• Probing the equilibrium dynamics of colloidal hard spheres above the mode-coupling glass transition
• Comparative simulation study of colloidal gels and glasses
• Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. I. General Formulation and Application to Hard Sphere Fluids
• Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. II. Thermal Liquids
• Nonperturbative effect of attractive forces in viscous liquids
• Growing point-to-set length scale correlates with growing relaxation times in model supercooled liquids
• Why are glass-forming liquids non-Arrhenius?
• Unified Theory of Activated Relaxation in Liquids over 14 Decades in Time
• A repulsive reference potential reproducing the dynamics of a liquid with attractions
• Corresponding States of Structural Glass Formers. II
• The role of attractive forces in viscous liquids
• A critical test of the mode-coupling theory of the glass transition
• Testing "microscopic" theories of glass-forming liquids
• Static triplet correlations in glass-forming liquids: A molecular dynamics study
• Do the repulsive and attractive pair forces play separate roles for the physics of liquids?

Cited by in corpus (18)

• Attractive versus truncated repulsive supercooled liquids: The dynamics is encoded in the pair correlation function
• Nonmonotonic behavior in the dense assemblies of active colloids
• Equation of State and Entropy Theory Approach to Thermodynamic Scaling in Polymeric Glass-Forming Liquids
• Theory of the Spatial Transfer of Interface-Nucleated Changes of Dynamical Constraints and Its Consequences in Glass-Forming Films
• A Microscopic Theory of Softness in Supercooled Liquids
• Theory of Activated Glassy Dynamics in Randomly Pinned Fluids
• Role of attractive forces in the relaxation dynamics of supercooled liquids
• Microscopic Theory of the Influence of Strong Attractive Forces on the Activated Dynamics of Dense Glass and Gel Forming Fluids
• Segment-Scale, Force-Level Theory of Mesoscopic Dynamic Localization and Entropic Elasticity in Entangled Chain Polymer Liquids
• Multi-component generalized mode-coupling theory: Predicting dynamics from structure in glassy mixtures
• Comparing four hard-sphere approximations for the low-temperature WCA melting line
• Self-averaging fluctuations in the chaoticity of simple fluids
• Generalized Mode-Coupling Theory for Mixtures of Brownian Particles
• How attractive and repulsive interactions affect structure ordering and dynamics of glass-forming liquids?
• Microscopic Theory of Onset of De-Caging and Bond Breaking Activated Dynamics in Ultra-Dense Fluids with Strong Short Range Attractions
• Microscopic Theory of the Elastic Shear Modulus and Length-Scale-Dependent Dynamic Re-Entrancy Phenomena in Very Dense Sticky Particle Fluids
• Comparing zero-parameter theories for the WCA and harmonic-repulsive melting lines
• Elastically Collective Nonlinear Langevin Equation Theory of Dynamics in Glass-Forming Liquids: Transient Localization, Thermodynamic Mapping and Cooperativity