A general microscopic and macroscopic theory is developed for systems which are governed by a (linear) master equation. The theory is based on a network representation of the master equation, and the results are obtained mostly by application of some basic theorems of mathematical graph theory. In the microscopic part of the theory, the construction of a steady state solution of the master equation in terms of graph theoretical elements is described (Kirchhoff's theorem), and it is shown that the master equation satisfies a global asymptotic Liapunov stability criterion with respect to this state. The Glansdorff-Prigogine criterion turns out to be the differential version and thus a special case of the global criterion. In the macroscopic part of the theory, a general prescription is given describing macrostates of the systems arbitrarily far from equilibrium in the language of generalized forces and fluxes of nonlinear irreversible thermodynamics. As a particular result, Onsager's reciprocity relations for the phenomenological coefficients are obtained as coinciding with the reciprocity relations of a near-to-equilibrium network.

DOI:https://doi.org/10.1103/RevModPhys.48.571