Detailed balance means that at thermodynamic equilibrium each elementary transition and its reverse carry equal probability flux. For normalized state probabilities and ,With the printed convention , the sign is thereforeThe values are free energies per system, including internal degeneracies; for molar Gibbs free energies, replace by . If B has lower free energy, its forward-to-reverse rate ratio exceeds one, as it should.
For constant rates, conservation gives , so the master equation is . Its steady state is , and separation of the decaying deviation yieldsfor the specified initial state A. The relaxation time constant is .
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