Liquids near the glass transition exhibit dynamical heterogeneity, i.e., correlated regions in the liquid relax at either a much faster rate or a much slower rate than the average. This collective phenomenon has been characterized by measurements of a dynamic susceptibility χ_{4}(t), which is sometimes interpreted in terms of the size of those relaxing regions and the intensity of the fluctuations. We show that the results of those measurements can be affected not only by the collective fluctuations in the relaxation rate, but also by density fluctuations in the initial state and by single-particle fluctuations. We also show that at very long times the average overlap C(t) probing the similarity between an initial and a final state separated by a time interval t decays as a power law C(t)∼t^{-d/2}. This is much slower than the stretched exponential behavior C(t)∼e^{-(t/τ)^{β}} previously observed at times within one or two orders of magnitude of the α-relaxation time τ_{α}. We find that for times longer than 10-100τ_{α}, the dynamic susceptibility χ_{4}(t) is dominated by single-particle fluctuations, and that χ_{4}(t)≈C(t)∼t^{-d/2}. Finally, we introduce a method to extract the collective relaxation contribution to the dynamic susceptibility χ_{4}(t) by subtracting the effects of single-particle fluctuations and initial state density fluctuations. We apply this method to numerical simulations of two glass-forming models: a binary hard sphere system and a Kob-Andersen Lennard-Jones system. This allows us to extend the analysis of numerical data to timescales much longer than previously possible, and opens the door for further future progress in the study of dynamic heterogeneities, including the determination of the exchange time.
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http://dx.doi.org/10.1103/PhysRevE.105.014605 | DOI Listing |
ACS Nano
January 2025
Department of Chemistry, Indiana University, Bloomington, Indiana 47405, United States.
Nature
January 2025
Max-Planck-Institut für Quantenoptik, Garching, Germany.
J Chem Theory Comput
December 2024
Materials Science Department, Graduate School of Engineering, Chiba University, Chiba 263-8522, Japan.
The standard definition of particle number fluctuations based on point-like particles neglects the excluded volume effect. This leads to a large and systematic finite-size scaling and an unphysical surface term in the isothermal compressibility. We correct these errors by introducing a modified pair distribution function that takes account of the finite size of the particles.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
Department of Biomedical Engineering, Eindhoven University of Technology, Eindhoven, 5612 AZ, The Netherlands.
Biomolecular sensors with single-molecule resolution are composed of multitudes of transducers that measure state changes related to single-molecular binding and unbinding events. Conventionally, signals are aggregated from many individual transducers in order to achieve sufficient statistics. However, by aggregating signals, transducer-to-transducer differences are lost and heterogeneities cannot be studied.
View Article and Find Full Text PDFJ Phys Chem B
December 2024
Laboratoire Charles Coulomb (L2C), Université de Montpellier, CNRS, 34095 Montpellier, France.
The swap Monte Carlo algorithm introduces nonphysical dynamic rules to accelerate the exploration of the configuration space of supercooled liquids. Its success raises deep questions regarding the nature and physical origin of the slow dynamics of dense liquids and how it is affected by swap moves. We provide a detailed analysis of the slow dynamics generated by the swap Monte Carlo algorithm at very low temperatures in two glass-forming models.
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