Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 121, Issue 13, Pages 6167-6174Publisher
AMER INST PHYSICS
DOI: 10.1063/1.1782391
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The Onsager and higher-order reciprocity relations are derived from a fluctuation theorem for nonequilibrium reactions ruled by the chemical master equation. The fluctuation theorem is obtained for the generating function of the macroscopic fluxes between chemiostats maintaining the system in a nonequilibrium steady state. The macroscopic affinities associated with the fluxes are identified by graph theory. The Yamamoto-Zwanzig formulas for the reaction constants are also derived from the fluctuation theorem. (C) 2004 American Institute of Physics.
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