Studying the Brownian motion of a system driven by an external control from one macroscopic state to another macroscopic state, this paper presents the derivation of a nonlinear fluctuation-dissipation theorem (FDT). The new FDT relates the nonequilibrium work to the equilibrium free-energy difference in a very simple manner. It is valid wherever the Brownian dynamics is applicable. It recovers the well-known Crooks fluctuation theorem (CFT) within the quasiequilibrium regime where the dissipative work is nearly zero. It will also be shown that the CFT’s fundamental assumption of microscopic reversibility is not obeyed in experiments such as mechanically unfolding biological molecules, in which the external driving forces depend on the system’s coordinates.
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14 October 2008
Research Article|
October 14 2008
Nonequilibrium fluctuation-dissipation theorem of Brownian dynamics
L. Y. Chen
L. Y. Chen
a)
Department of Physics,
University of Texas at San Antonio
, San Antonio, Texas 78249, USA
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a)
Electronic mail: [email protected].
J. Chem. Phys. 129, 144113 (2008)
Article history
Received:
August 21 2008
Accepted:
September 10 2008
Citation
L. Y. Chen; Nonequilibrium fluctuation-dissipation theorem of Brownian dynamics. J. Chem. Phys. 14 October 2008; 129 (14): 144113. https://doi.org/10.1063/1.2992153
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