Cooperativity and the freezing of molecular motion at the glass transition

Abstract

The slowing down of molecular dynamics when approaching the glass transition generally proceeds much stronger than expected for thermally activated motions. This strange phenomenon can be formally ascribed to a temperature-dependent activation energy E(T). In the present work, via measurements of the third-order nonlinear dielectric susceptibility, we deduce the increase of the number of correlated molecules Ncorr when approaching the glass transition and find a surprisingly simple correlation of E(T) and Ncorr(T). This provides strong evidence that the non-canonical temperature development of glassy dynamics is caused by a temperature-dependent energy barrier arising from the cooperative motion of ever larger numbers of molecules at low temperatures.

5 pages (including 2 pages Supplemental Material), 4 + 3 figures Final revised version according to suggestions of referees

References in corpus (2)

• Temperature development of glassy alpha-relaxation dynamics determined by broadband dielectric spectroscopy
• Nonlinear dielectric response at the excess wing of glass-forming liquids

Cited by in corpus (46)

• The role of local structure in dynamical arrest
• Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers
• 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
• Thermal expansion and the glass transition
• Universal features of dynamic heterogeneity in supercooled liquids
• Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing
• Orientationally Glassy Crystals of Janus Spheres
• A new view of the Lindemann criterion
• Qualitative Features at the Glass Crossover
• Dynamic Correlation Length Scales under Isochronal Conditions
• Emergence of non-equilibrium charge dynamics in a charge-cluster glass
• The nature of geometric frustration in the Kob-Andersen mixture
• Cooperativity and Heterogeneity in Plastic Crystals Studied by Nonlinear Dielectric Spectroscopy
• Glycerol confined in zeolitic imidazolate frameworks: The temperature-dependent cooperativity length scale of glassy freezing
• Nonlinear dielectric spectroscopy in a fragile plastic crystal
• Origin of the glass-like dynamics in molecular metals $\kappa$-(BEDT-TTF)${}_{\text{2}}$X: implications from fluctuation spectroscopy and $\text{ab initio}$ calculations
• Investigation of nonlinear effects in glassy matter using dielectric methods
• Disentangling interatomic repulsion and anharmonicity in the viscosity and fragility of glasses
• Orbital-Order Driven Ferroelectricity and Dipolar Relaxation Dynamics in Multiferroic GaMo${}_4$S${}_8$
• Nonlinear dielectric response of Debye, alpha, and beta relaxation in 1-propanol
• The glass transition in molecules, colloids and grains: universality and specificity
• Unifying different interpretations of the nonlinear response in glass-forming liquids
• Correlation between crystalline order and vitrification in colloidal monolayers
• MFU-type metal-organic frameworks as host materials of confined supercooled liquids
• Low temperature dielectric relaxation study of aqueous solutions of diethylsulfoxide
• Nonlinear response theory for Markov processes II: Fifth-order response functions
• Glassy Dynamics from First-Principles Simulations
• Dynamical Susceptibilities Near Ideal Glass Transitions
• Involvement of structural dynamics in the charge-glass formation in molecular metals
• Fragile-to-Strong Crossover, growing length scales, and dynamic heterogeneity in Wigner Glasses
• Eshelby description of highly viscous flow -- half model, half theory
• Manipulating the Glass Transition in Nanoscale
• Third and Fifth Harmonic Responses in Viscous Liquids
• Discovery of a paired Gaussian and long-tailed distribution of potential energies in nanoglasses
• Johari-Goldstein relaxation in glass-electrets
• Crystal melting influenced by particle cooperativity of the liquid
• Magneto-thermally Activated Spin-state Transition in La0.95Ca0.05CoO3: Magnetically-tunable Dipolar Glass and Giant Magneto-electricity
• Structural relaxation and highly viscous flow
• Emergence of a Hump in the Cubic Dielectric Response of Glycerol
• Nonlinear dielectric response in glasses: restoring forces and avoided spin-glass criticality
• Third order dielectric time dependent susceptibilities and the 'Box Model'
• Combined experimental and theoretical studies on glasslike transitions in the frustrated molecular conductors $\theta$-(BEDT-TTF)${}_{2}M{M}^{\prime }$(SCN)${}_4$
• The 2/3 Rule of Glass Physics Implies Universalities in Crystal Melting
• Amorphous Order & Non-linear Susceptibilities in Glassy Materials
• Prigogine-Defay ratio of glassy freezing scales with liquid fragility