An official website of the United States government
The global steady state of a system in thermal equilibrium exponentially favors configurations with lesser energy. This principle is a powerful explanation of self-organization because energy is a local property of configurations. For nonequilibrium systems, there is no such property for which an analogous principle holds, hence no common explanation of the diverse forms of self-organization they exhibit. However, a flurry of recent empirical results has shown that a local property of configurations called “rattling” predicts the steady states of some nonequilibrium systems, leading to claims of a far-reaching principle of nonequilibrium self-organization. But for which nonequilibrium systems is rattling accurate, and why? We develop a theory of rattling in terms of Markov processes that gives simple and precise answers to these key questions. Our results show that rattling predicts a broader class of nonequilibrium steady states than has been claimed and for different reasons than have been suggested. Its predictions hold to an extent determined by the relative variance of, and correlation between, the local and global “parts” of a steady state. We show how these quantities characterize the local-global relationships of various random walks on random graphs, spin-glass dynamics, and models of animal collective behavior. Surprisingly, we find that the core idea of rattling is so general as to apply to equilibrium and nonequilibrium systems alike.
more »
« less
Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis
Nonequilibrium work relations have fundamentally advanced our understanding of molecular processes. In recent years, fluctuation theorems have been extensively applied to understand transitions between equilibrium steady-states, commonly described by simple control parameters such as molecular extension of a protein or polymer chain stretched by an external force in a quiescent fluid. Despite recent progress, far less is understood regarding the application of fluctuation theorems to processes involving nonequilibrium steady-states such as those described by polymer stretching dynamics in nonequilibrium fluid flows. In this work, we apply the Crooks fluctuation theorem to understand the nonequilibrium thermodynamics of dilute polymer solutions in flow. We directly determine the nonequilibrium free energy for single polymer molecules in flow using a combination of single molecule experiments and Brownian dynamics simulations. We further develop a time-dependent extensional flow protocol that allows for probing viscoelastic hysteresis over a wide range of flow strengths. Using this framework, we define quantities that uniquely characterize the coil-stretch transition for polymer chains in flow. Overall, generalized fluctuation theorems provide a powerful framework to understand polymer dynamics under far-from-equilibrium conditions.
more »
« less
- PAR ID:
- 10389188
- Date Published:
- Journal Name:
- Entropy
- Volume:
- 24
- Issue:
- 1
- ISSN:
- 1099-4300
- Page Range / eLocation ID:
- 27
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract We analyze the static response to kinetic perturbations of nonequilibrium steady states that can be modeled as diffusions. We demonstrate that kinetic response is purely a nonequilibirum effect, measuring the degree to which the Fluctuation-Dissipation Theorem is violated out of equilibrium. For driven diffusions in a flat landscape, we further demonstrate that such response is constrained by the strength of the nonequilibrium driving via quantitative inequalities.more » « less
-
Diverse chemical, energy, environmental, and industrial processes involve the flow of polymer solutions in porous media. The accumulation and dissipation of elastic stresses as the polymers are transported through the tortuous, confined pore space can lead to the development of an elastic flow instability above a threshold flow rate, producing a transition from steady to unsteady flow characterized by strong spatiotemporal fluctuations, despite the low Reynolds number (Re≪1). Furthermore, in 1D ordered arrays of pore constrictions, this unsteady flow can undergo a second transition to multistability, where distinct pores simultaneously exhibit distinct unsteady flow states. Here, we examine how this transition to multistability is influenced by fluid rheology. Through experiments using diverse polymer solutions having systematic variations in fluid shear-thinning or elasticity, in pore constriction arrays of varying geometries, we show that the onset of multistability can be described using a single dimensionless parameter, given sufficient fluid elasticity. This parameter, the streamwise Deborah number, compares the stress relaxation time of the polymer solution to the time required for the fluid to be advected between pore constrictions. Our work thus helps to deepen understanding of the influence of fluid rheology on elastic instabilities, helping to establish guidelines for the rational design of polymeric fluids with desirable flow behaviors.more » « less
-
We use a nonequilibrium variational principle to optimize the steady-state, shear-induced interconversion of self-assembled nanoclusters of DNA-coated colloids. Employing this principle within a stochastic optimization algorithm allows us to identify design strategies for functional materials. We find that far-from-equilibrium shear flow can significantly enhance the flux between specific colloidal states by decoupling trade-offs between stability and reactivity required by systems in equilibrium. For isolated nanoclusters, we find nonequilibrium strategies for amplifying transition rates by coupling a given reaction coordinate to the background shear flow. We also find that shear flow can be made to selectively break detailed balance and maximize probability currents by coupling orientational degrees of freedom to conformational transitions. For a microphase consisting of many nanoclusters, we study the flux of colloids hopping between clusters. We find that a shear flow can amplify the flux without a proportional compromise on the microphase structure. This approach provides a general means of uncovering design principles for nanoscale, autonomous, functional materials driven far from equilibrium.more » « less
-
We study diffusion-controlled processes in nonequilibrium steady states, where standard rate theory assumptions break down. Using transition path theory, we generalize the relations between reactive probability fluxes and measures of the rate of the reaction. Stochastic thermodynamics analysis reveals how work constrains the enhancement of rates relative to their equilibrium values. An analytically solvable ion pairing model under a strong electric field illustrates and validates our approach and theory. These findings provide deeper insights into diffusion-controlled reaction dynamics beyond equilibrium.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/e24010027
