Prevalence of multistability and nonstationarity in driven chemical networks.

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.

Typical Stochastic Paths in the Transient Assembly of Fibrous Materials.

When chemically fueled, molecular self-assembly can sustain dynamic aggregates of polymeric fibers-hydrogels-with tunable properties. If the fuel supply is finite, the hydrogel is transient, as competing reactions switch molecular subunits between active and inactive states, drive fiber growth and collapse, and dissipate energy. Because the process is away from equilibrium, the structure and mechanical properties can reflect the history of preparation. As a result, the formation of these active materials is not readily susceptible to a statistical treatment in which the configuration and properties of the molecular building blocks specify the resulting material structure. Here, we illustrate a stochastic-thermodynamic and information-theoretic framework for this purpose and apply it to these self-annihilating materials. Among the possible paths, the framework variationally identifies those that are typical-loosely, the minimum number with the majority of the probability. We derive these paths from computer simulations of experimentally-informed stochastic chemical kinetics and a physical kinetics model for the growth of an active hydrogel. The model reproduces features observed by confocal microscopy, including the fiber length, lifetime, and abundance as well as the observation of fast fiber growth and stochastic fiber collapse. The typical mesoscopic paths we extract are less than 0.23% of those possible, but they accurately reproduce material properties such as mean fiber length.

Entrance and escape dynamics for the typical set.

According to the asymptotic equipartition property, sufficiently long sequences of random variables converge to a set that is typical. While the size and probability of this set are central to information theory and statistical mechanics, they can often only be estimated accurately in the asymptotic limit due to the exponential growth in possible sequences. Here we derive a time-inhomogeneous dynamics that constructs the properties of the typical set for all finite length sequences of independent and identically distributed random variables. These dynamics link the finite properties of the typical set to asymptotic results and allow the typical set to be applied to small and transient systems. The main result is a geometric mapping-the triangle map-relating sequences of random variables of length n to those of length n+1. We show that the number of points in this map needed to quantify the properties of the typical set grows linearly with sequence length, despite the exponential growth in the number of typical sequences. We illustrate the framework for the Bernoulli process and the Schlögl model for autocatalytic chemical reactions and demonstrate both the convergence to asymptotic limits and the ability to reproduce exact calculations.

Effects of temperature and mass conservation on the typical chemical sequences of hydrogen oxidation.

Macroscopic properties of reacting mixtures are necessary to design synthetic strategies, determine yield, and improve the energy and atom efficiency of many chemical processes. The set of time-ordered sequences of chemical species are one representation of the evolution from reactants to products. However, only a fraction of the possible sequences is typical, having the majority of the joint probability and characterizing the succession of chemical nonequilibrium states. Here, we extend a variational measure of typicality and apply it to atomistic simulations of a model for hydrogen oxidation over a range of temperatures. We demonstrate an information-theoretic methodology to identify typical sequences under the constraints of mass conservation. Including these constraints leads to an improved ability to learn the chemical sequence mechanism from experimentally accessible data. From these typical sequences, we show that two quantities defining the variational typical set of sequences-the joint entropy rate and the topological entropy rate-increase linearly with temperature. These results suggest that, away from explosion limits, data over a narrow range of thermodynamic parameters could be sufficient to extrapolate these typical features of combustion chemistry to other conditions.

Learning the mechanisms of chemical disequilibria.

When at equilibrium, large-scale systems obey thermodynamics because they have microscopic configurations that are typical. "Typical" states are a fraction of those possible with the majority of the probability. A more precise definition of typical states underlies the transmission, coding, and compression of information. However, this definition does not apply to natural systems that are transiently away from equilibrium. Here, we introduce a variational measure of typicality and apply it to atomistic simulations of a model for hydrogen oxidation. While a gaseous mixture of hydrogen and oxygen combusts, reactant molecules transform through a variety of ephemeral species en route to the product, water. Out of the exponentially growing number of possible sequences of chemical species, we find that greater than 95% of the probability concentrates in less than 1% of the possible sequences. Overall, these results extend the notion of typicality across the nonequilibrium regime and suggest that typical sequences are a route to learning mechanisms from experimental measurements. They also open up the possibility of constructing ensembles for computing the macroscopic observables of systems out of equilibrium.