We introduce two new concepts of convergence of gradient systems $$({\mathbf{Q}}, {{\mathcal {E}}}_\varepsilon ,{{\mathcal {R}}}_\varepsilon )$$ ( Q , E ε , R ε ) to a limiting gradient system $$({\mathbf{Q}},{{\mathcal {E}}}_0,{{\mathcal {R}}}_0)$$ ( Q , E 0 , R 0 ) . These new concepts are called ‘EDP convergence with tilting’ and ‘contact–EDP convergence with tilting.’ Both are based on the energy-dissipation-principle (EDP) formulation of solutions of gradient systems and can be seen as refinements of the Gamma-convergence for gradient flows first introduced by Sandier and Serfaty. The two new concepts are constructed in order to avoid the ‘unnatural’ limiting gradient structures that sometimes arise as limits in EDP convergence. EDP convergence with tilting is a strengthening of EDP convergence by requiring EDP convergence for a full family of ‘tilted’ copies of $$({\mathbf{Q}}, {{\mathcal {E}}}_\varepsilon ,{{\mathcal {R}}}_\varepsilon )$$ ( Q , E ε , R ε ) . It avoids unnatural limiting gradient structures, but many interesting systems are non-convergent according to this concept. Contact–EDP convergence with tilting is a relaxation of EDP convergence with tilting and still avoids unnatural limits but applies to a broader class of sequences $$({\mathbf{Q}}, {{\mathcal {E}}}_\varepsilon ,{{\mathcal {R}}}_\varepsilon )$$ ( Q , E ε , R ε ) . In this paper, we define these concepts, study their properties, and connect them with classical EDP convergence. We illustrate the different concepts on a number of test problems.

By reformulating the steepest-entropy-ascent (SEA) dynamical model for nonequilibrium thermodynamics in the mathematical language of differential geometry, we compare it with the primitive formulation of the general equation for the nonequilibrium reversible-irreversible coupling (GENERIC) model and discuss the main technical differences of the two approaches. In both dynamical models the description of dissipation is of the "entropy-gradient" type. SEA focuses only on the dissipative, i.e., entropy generating, component of the time evolution, chooses a sub-Riemannian metric tensor as dissipative structure, and uses the local entropy density field as potential. GENERIC emphasizes the coupling between the dissipative and nondissipative components of the time evolution, chooses two compatible degenerate structures (Poisson and degenerate co-Riemannian), and uses the global energy and entropy functionals as potentials. As an illustration, we rewrite the known GENERIC formulation of the Boltzmann equation in terms of the square root of the distribution function adopted by the SEA formulation. We then provide a formal proof that in more general frameworks, whenever all degeneracies in the GENERIC framework are related to conservation laws, the SEA and GENERIC models of the dissipative component of the dynamics are essentially interchangeable, provided of course they assume the same kinematics. As part of the discussion, we note that equipping the dissipative structure of GENERIC with the Leibniz identity makes it automatically SEA on metric leaves.

Understanding the fluctuations by which phenomenological evolution equations with thermodynamic structure can be enhanced is the key to a general framework of nonequilibrium statistical mechanics. These fluctuations provide an idealized representation of microscopic details. We consider fluctuation-enhanced equations associated with Markov processes and elaborate the general recipes for evaluating dynamic material properties, which characterize force-flux constitutive laws, by statistical mechanics. Markov processes with continuous trajectories are conveniently characterized by stochastic differential equations and lead to Green–Kubo-type formulas for dynamic material properties. Markov processes with discontinuous jumps include transitions over energy barriers with the rates calculated by Kramers. We describe a unified approach to Markovian fluctuations and demonstrate how the appropriate type of fluctuations (continuous versus discontinuous) is reflected in the mathematical structure of the phenomenological equations.

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For a given thermodynamic system, and a given choice of coarse-grained state variables, the knowledge of a force-flux constitutive law is the basis for any nonequilibrium modeling. In the first paper of this series we established how, by a generalization of the classical fluctuation-dissipation theorem (FDT), the structure of a constitutive law is directly related to the distribution of the fluctuations of the state variables. When these fluctuations can be expressed in terms of diffusion processes, one may use Green–Kubo-type coarse-graining schemes to find the constitutive laws. In this paper we propose a coarse-graining method that is valid when the fluctuations are described by means of general Markov processes, which include diffusions as a special case. We prove the success of the method by numerically computing the constitutive law for a simple chemical reaction A\rightleftarrows B. Furthermore, we show that, for such a system, one cannot find a consistent constitutive law by any Green–Kubo-like scheme.