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Equation 14 · From Origins to Frontier: A History of Stochastic Thermodynamics and Complex Systems

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kBTk_BT

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kBk_B

Symbol k_B

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TT

Symbol T

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subscript

subscript

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In 2002, Jan Liphardt, Sophie Dumont, Steven Smith, Ignacio Tinoco Jr, and Carlos Bustamante published “Equilibrium Information from Nonequilibrium Measurements in an Experimental Test of Jarzynski’s Equality” in Science [ 5 ] . They used optical tweezers to unfold and refold a single RNA hairpin molecule repeatedly, at speeds fast enough that the process was thermodynamically irreversible on each individual repetition, then applied the Jarzynski average to recover the equilibrium free energy of unfolding — and found it agreed with the independently measured equilibrium value to within about half of kBk_BT . This was the first direct experimental confirmation that Jarzynski’s exponential…
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In 2002, Jan Liphardt, Sophie Dumont, Steven Smith, Ignacio Tinoco Jr, and Carlos Bustamante published “Equilibrium Information from Nonequilibrium Measurements in an Experimental Test of Jarzynski’s Equality” in Science [ 5 ] . They used optical tweezers to unfold and refold a single RNA hairpin molecule repeatedly, at speeds fast enough that the process was thermodynamically irreversible on each individual repetition, then applied the Jarzynski average to recover the equilibrium free energy of unfolding — and found it agreed with the independently measured equilibrium value to within about half of kBk_BT . This was the first direct experimental confirmation that Jarzynski’s exponential average genuinely recovers equilibrium thermodynamic quantities from nonequilibrium single-molecule trajectories, rather than being a purely formal identity with no practical purchase.

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