Scaling down the laws of thermodynamics
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Thermodynamics provides a robust conceptual framework and set of laws that govern the exchange of energy and matter. Although these laws were originally articulated for macroscopic objects, it is hard to deny that nanoscale systems, as well, often exhibit “thermodynamic-like” behavior. To what extent can the venerable laws of thermodynamics be scaled down to apply to individual microscopic systems, and what new features emerge at the nanoscale? I will review recent progress toward answering these questions, with a focus on the second law of thermodynamics. I will argue that the inequalities ordinarily used to express the second law can be replaced by stronger equalities, known as fluctuation relations, which relate equilibrium properties to far-from-equilibrium fluctuations. The discovery and experimental validation of these relations has stimulated interest in the feedback control of small systems, the closely related Maxwell demon paradox, and the interpretation of the thermodynamic arrow of time. These developments have led to new tools for the analysis of non-equilibrium experiments and simulations, and they have refined our understanding of irreversibility and the second law.
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