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Equation 12 · From Origins to Frontier: A History of Stochastic Thermodynamics and Complex Systems

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−W-W

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WW

Symbol W

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This is a striking claim on its face: it says a quantity defined only for reversible, quasistatic processes — a free energy difference — can be computed from measurements of an irreversible process, no matter how fast or violent the driving, provided enough repetitions are averaged. Two years later, Gavin Crooks derived a closely related and in some respects more general result, the Crooks fluctuation theorem, in “Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences,” published in Physical Review E in 1999 [ 4 ] . Crooks’s relation compares the probability of observing work W in a forward protocol to the probability of observing -W in the…
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This is a striking claim on its face: it says a quantity defined only for reversible, quasistatic processes — a free energy difference — can be computed from measurements of an irreversible process, no matter how fast or violent the driving, provided enough repetitions are averaged. Two years later, Gavin Crooks derived a closely related and in some respects more general result, the Crooks fluctuation theorem, in “Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences,” published in Physical Review E in 1999 [ 4 ] . Crooks’s relation compares the probability of observing work W in a forward protocol to the probability of observing -W in the corresponding time-reversed protocol:

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