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Thermodynamic speed limits are a set of classical uncertainty relations that, so far, place global bounds on the stochastic dissipation of energy as heat and the production of entropy. Here, instead of constraints on these thermodynamic costs, we derive integral speed limits that are upper and lower bounds on a thermodynamic benefit—the minimum time for an amount of mechanical work to be done on or by a system. In the short time limit, we show how this extrinsic timescale relates to an intrinsic timescale for work, recovering the intrinsic timescales in differential speed limits from these integral speed limits and turning the first law of stochastic thermodynamics into a first law of speeds. As physical examples, we consider the work done by a flashing Brownian ratchet and the work done on a particle in a potential well subject to external driving.

 

External flows of energy, entropy, and matter can cause sudden transitions in the stability of biological and industrial systems, fundamentally altering their dynamical function. How might we control and design these transitions in chemical reaction networks? Here, we analyze transitions giving rise to complex behavior in random reaction networks subject to external driving forces. In the absence of driving, we characterize the uniqueness of the steady state and identify the percolation of a giant connected component in these networks as the number of reactions increases. When subject to chemical driving (influx and outflux of chemical species), the steady state can undergo bifurcations, leading to multistability or oscillatory dynamics. By quantifying the prevalence of these bifurcations, we show how chemical driving and network sparsity tend to promote the emergence of these complex dynamics and increased rates of entropy production. We show that catalysis also plays an important role in the emergence of complexity, strongly correlating with the prevalence of bifurcations. Our results suggest that coupling a minimal number of chemical signatures with external driving can lead to features present in biochemical processes and abiogenesis. 

Living systems are built from microscopic components that function dynamically; they generate work with molecular motors, assemble and disassemble structures such as microtubules, keep time with circadian clocks, and catalyze the replication of DNA. How do we implement these functions in synthetic nanostructured materials to execute them before the onset of dissipative losses? Answering this question requires a quantitative understanding of when we can improve performance and speed while minimizing the dissipative losses associated with operating in a fluctuating environment. Here, we show that there are four modalities for optimizing dynamical functions that can guide the design of nanoscale systems. We analyze Markov models that span the design space: a clock, ratchet, replicator, and self-assembling system. Using stochastic thermodynamics and an exact expression for path probabilities, we classify these models of dynamical functions based on the correlation of speed with dissipation and with the chosen performance metric. We also analyze random networks to identify the model features that affect their classification and the optimization of their functionality. Overall, our results show that the possible nonequilibrium paths can determine our ability to optimize the performance of dynamical functions, despite ever-present dissipation, when there is a need for speed. 

Physical kinetic roughening processes are well-known to exhibit universal scaling of observables that fluctuate in space and time. Are there analogous dynamic scaling laws that are unique to the chemical reaction mechanisms available synthetically and occurring naturally? Here, we formulate an approach to the dynamic scaling of stochastic fluctuations in thermodynamic observables at and away from equilibrium. Both analytical expressions and numerical simulations confirm our dynamic scaling ansatz with associated scaling exponents, function, and law. A survey of common chemical mechanisms reveals classes that organize according to the molecularity of the reactions involved, the nature of the reaction vessel and external reservoirs, (non)equilibrium conditions, and the extent of autocatalysis in the reaction network. Varying experimental parameters, such as temperature, can cause coupled reactions capable of chemical feedback to transition between these classes. While path observables, such as the dynamical activity, have scaling exponents that are time-independent, the variance in the entropy production and flow can have time-dependent scaling exponents and self-averaging properties as a result of temporal correlations that emerge during thermodynamically irreversible processes. Altogether, these results establish dynamic universality classes in the nonequilibrium fluctuations of thermodynamic observables for well-mixed chemical reactions.