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Equation 13 · From Origins to Frontier: A History of Stochastic Thermodynamics and Complex Systems

What does this equation mean?

PF(W)PR(−W)=e(W−ΔF)/kBT\frac{P_F(W)}{P_R(-W)} = e^{(W-\Delta F)/k_B T}

Read the formula alongside the article passage below. Each part has a deeper page with its role in the equation, the supporting passage and nearby citations.

Inputs and operationse^(W-Δ F)/k_B T
Result or conditionfracP_F(W)P_R(-W)
How to read the two sides of this formula. Follow the article passage for the meaning of each quantity.

This equation states an equality: the expressions on both sides have the same value under the article’s assumptions. Read the equation part by part below; each part has a contextual explanation and a link to its mathematical background.

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PFP_F

Symbol P_F

PFP_F occurs above the fraction bar. The numerator is divided by the entire denominator below it.

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WW

Symbol W

W is an argument of the function-like quantity on the left; its role is set by that function’s stated inputs.

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PRP_R

Symbol P_R

PRP_R occurs below the fraction bar. The quantity above the bar is divided by this expression; zero is excluded as a denominator.

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e(W−ΔF)/kBTe^{(W-\Delta F)/k_B T}

Symbol e^(W-Δ F)/k_B T

e^(W-Δ F)/kBk_B T is one of the signed contributions combined to compute the quantity on the left.

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=

=

The expressions on both sides represent the same quantity under the stated assumptions.

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fraction

fraction

Divide the expression above the line by the one below it.

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subtraction

subtraction

Subtract the following term or group from the preceding one. A leading minus marks a negative quantity.

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change

change

Capital delta attached to a quantity marks a difference between two values of that quantity; the article’s sign convention determines the order.

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subscript

subscript

The lower label selects a particular version, component, or indexed member of the quantity. For example, x₀ and xₜ can be values at different positions.

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superscript

superscript

A raised number can be a power. When it is a label or bound, it selects a case or the upper limit of a sum; the formula’s structure distinguishes these uses.

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PF(W)P_F(W)

Numerator: P_F(W)

The complete quantity above the fraction bar.

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PR(−W)P_R(-W)

Denominator: P_R(-W)

The complete quantity below the fraction bar; it must be nonzero for this division.

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How to interpret it

With a fixed numerator, increasing a nonzero denominator reduces the fraction. Read it with the definitions, units, and assumptions supplied by the article.

What the article says around this equation

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: PF(W)PR(−W)=e(W−ΔF)/kBT\frac{P_F(W)}{P_R(-W)} = e^{(W-\Delta F)/k_B T}. The Jarzynski equality follows from the Crooks relation as a special case, and both are instances of a broader family of fluctuation theorems that had been developing since Denis Evans, E. G. D. Cohen, and G. P. Morriss’s 1993 work on fluctuation theorems in shearing steady states. What made Jarzynski’s and Crooks’s results different from that broader family was specificity and testability: they made a sharp, falsifiable numerical prediction about a quantity — work performed on a driven system — that single-molecule experimentalists were, by the late 1990s, on the verge of being able to measure directly with laser tweezers and atomic force microscopes.

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Sources cited in the surrounding passage

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