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1. A statistical mechanics framework for constructing nonequilibrium thermodynamic models

   https://doi.org/10.1093/pnasnexus/pgad417  

   Leadbetter, Travis; Purohit, Prashant K; Reina, Celia (December 2023, PNAS Nexus)

   Sharma, Pradeep (Ed.)

   Far-from-equilibrium phenomena are critical to all natural and engineered systems, and essential to biological processes responsible for life. For over a century and a half, since Carnot, Clausius, Maxwell, Boltzmann, and Gibbs, among many others, laid the foundation for our understanding of equilibrium processes, scientists and engineers have dreamed of an analogous treatment of nonequilibrium systems. But despite tremendous efforts, a universal theory of nonequilibrium behavior akin to equilibrium statistical mechanics and thermodynamics has evaded description. Several methodologies have proved their ability to accurately describe complex nonequilibrium systems at the macroscopic scale, but their accuracy and predictive capacity is predicated on either phenomenological kinetic equations fit to microscopic data or on running concurrent simulations at the particle level. Instead, we provide a novel framework for deriving stand-alone macroscopic thermodynamic models directly from microscopic physics without fitting in overdamped Langevin systems. The only necessary ingredient is a functional form for a parameterized, approximate density of states, in analogy to the assumption of a uniform density of states in the equilibrium microcanonical ensemble. We highlight this framework’s effectiveness by deriving analytical approximations for evolving mechanical and thermodynamic quantities in a model of coiled-coil proteins and double-stranded DNA, thus producing, to the authors’ knowledge, the first derivation of the governing equations for a phase propagating system under general loading conditions without appeal to phenomenology. The generality of our treatment allows for application to any system described by Langevin dynamics with arbitrary interaction energies and external driving, including colloidal macromolecules, hydrogels, and biopolymers. 

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2. Non-equilibrium early-warning signals for critical transitions in ecological systems

   https://doi.org/10.1073/pnas.2218663120  

   Xu, Li; Patterson, Denis; Levin, Simon Asher; Wang, Jin (January 2023, Proceedings of the National Academy of Sciences)

   Complex systems can exhibit sudden transitions or regime shifts from one stable state to another, typically referred to as critical transitions. It becomes a great challenge to identify a robust warning sufficiently early that action can be taken to avert a regime shift. We employ landscape-flux theory from nonequilibrium statistical mechanics as a general framework to quantify the global stability of ecological systems and provide warning signals for critical transitions. We quantify the average flux as the nonequilibrium driving force and the dynamical origin of the nonequilibrium transition while the entropy production rate as the nonequilibrium thermodynamic cost and thermodynamic origin of the nonequilibrium transition. Average flux, entropy production, nonequilibrium free energy, and time irreversibility quantified by the difference in cross-correlation functions forward and backward in time can serve as early warning signals for critical transitions much earlier than other conventional predictors. We utilize a classical shallow lake model as an exemplar for our early warning prediction. Our proposed method is general and can be readily applied to assess the resilience of many other ecological systems. The early warning signals proposed here can potentially predict critical transitions earlier than established methods and perhaps even sufficiently early to avert catastrophic shifts. 

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3. Nonequilibrium statistical thermodynamics of multicomponent interfaces

   https://doi.org/10.1073/pnas.2121405119  

   Rauscher, Phillip M.; Öttinger, Hans Christian; de Pablo, Juan J. (June 2022, Proceedings of the National Academy of Sciences)

   Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena. 

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4. Quantum entropy and central limit theorem

   https://doi.org/10.1073/pnas.2304589120  

   Bu, Kaifeng; Gu, Weichen; Jaffe, Arthur (June 2023, Proceedings of the National Academy of Sciences)

   We introduce a framework to study discrete-variable (DV) quantum systems based on qudits. It relies on notions of a mean state (MS), a minimal stabilizer-projection state (MSPS), and a new convolution. Some interesting consequences are: The MS is the closest MSPS to a given state with respect to the relative entropy; the MS is extremal with respect to the von Neumann entropy, demonstrating a “maximal entropy principle in DV systems.” We obtain a series of inequalities for quantum entropies and for Fisher information based on convolution, giving a “second law of thermodynamics for quantum convolutions.” We show that the convolution of two stabilizer states is a stabilizer state. We establish a central limit theorem, based on iterating the convolution of a zero-mean quantum state, and show this converges to its MS. The rate of convergence is characterized by the “magic gap,” which we define in terms of the support of the characteristic function of the state. We elaborate on two examples: the DV beam splitter and the DV amplifier. 

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5. Foundations of a finite non-equilibrium statistical thermodynamics: extrinsic quantities

   https://doi.org/10.1088/1751-8121/ac798a  

   Ericok, O B; Mason, J K (July 2022, Journal of Physics A: Mathematical and Theoretical)

   Abstract Statistical thermodynamics is valuable as a conceptual structure that shapes our thinking about equilibrium thermodynamic states. A cloud of unresolved questions surrounding the foundations of the theory could lead an impartial observer to conclude that statistical thermodynamics is in a state of crisis though. Indeed, the discussion about the microscopic origins of irreversibility has continued in the scientific community for more than a hundred years. This paper considers these questions while beginning to develop a statistical thermodynamics for finite non-equilibrium systems. Definitions are proposed for all of the extrinsic variables of the fundamental thermodynamic relation that are consistent with existing results in the equilibrium thermodynamic limit. The probability density function on the phase space is interpreted as a subjective uncertainty about the microstate, and the Gibbs entropy formula is modified to allow for entropy creation without introducing additional physics or modifying the phase space dynamics. Resolutions are proposed to the mixing paradox, Gibbs’ paradox, Loschmidt’s paradox, and Maxwell’s demon thought experiment. Finally, the extrinsic variables of the fundamental thermodynamic relation are evaluated as functions of time and space for a diffusing ideal gas, and the initial and final values are shown to coincide with the expected equilibrium values. 

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