This paper presents a study of the nonequilibrium relaxation process of chemically reactive systems using steepest-entropy-ascent quantum thermodynamics (SEAQT). The trajectory of the chemical reaction, i.e., the accessible intermediate states, is predicted and discussed. The prediction is made using a thermodynamic-ensemble approach, which does not require detailed information about the particle mechanics involved (e.g., the collision of particles). Instead, modeling the kinetics and dynamics of the relaxation process is based on the principle of steepest-entropy ascent (SEA) or maximum-entropy production, which suggests a constrained gradient dynamics in state space. The SEAQT framework is based on general definitions for energy and entropy and at least theoretically enables the prediction of the nonequilibrium relaxation of system state at all temporal and spatial scales. However, to make this not just theoretically but computationally possible, the concept of density of states is introduced to simplify the application of the relaxation model, which in effect extends the application of the SEAQT framework even to infinite energy eigenlevel systems. The energy eigenstructure of the reactive system considered here consists of an extremely large number of such levels (on the order of 10^{130}) and yields to the quasicontinuous assumption. The principle of SEA results in a unique trajectory of system thermodynamic state evolution in Hilbert space in the nonequilibrium realm, even far from equilibrium. To describe this trajectory, the concepts of subsystem hypoequilibrium state and temperature are introduced and used to characterize each system-level, nonequilibrium state. This definition of temperature is fundamental rather than phenomenological and is a generalization of the temperature defined at stable equilibrium. In addition, to deal with the large number of energy eigenlevels, the equation of motion is formulated on the basis of the density of states and a set of associated degeneracies. Their significance for the nonequilibrium evolution of system state is discussed. For the application presented, the numerical method used is described and is based on the density of states, which is specifically developed to solve the SEAQT equation of motion. Results for different kinds of initial nonequilibrium conditions, i.e., those for gamma and Maxwellian distributions, are studied. The advantage of the concept of hypoequilibrium state in studying nonequilibrium trajectories is discussed.

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This paper presents a nonequilibrium thermodynamic model for the relaxation of a local, isolated system in nonequilibrium using the principle of steepest entropy ascent (SEA), which can be expressed as a variational principle in thermodynamic state space. The model is able to arrive at the Onsager relations for such a system. Since no assumption of local equilibrium is made, the conjugate fluxes and forces, which result, are intrinsic to the subspaces of the system's state space and are defined using the concepts of hypoequilibrium state and nonequilibrium intensive properties, which describe the non-mutual equilibrium status between subspaces of the thermodynamic state space. The Onsager relations are shown to be a thermodynamic kinematic feature of the system independent of the specific details of the micro-mechanical dynamics. Two kinds of relaxation processes are studied with different constraints (i.e., conservation laws) corresponding to heat and mass diffusion. Linear behavior in the near-equilibrium region as well as nonlinear behavior in the far-from-equilibrium region are discussed. Thermodynamic relations in the equilibrium and nearequilibrium realm, including the Gibbs relation, the Clausius inequality, and the Onsager relations, are generalized to the far-from-equilibrium realm. The variational principle in the space spanned by the intrinsic conjugate fluxes and forces is expressed via the quadratic dissipation potential. As an application, the model is applied to the heat and mass diffusion of a system represented by a single particle ensemble, which can also be applied to a simple system of many particles. Phenomenological transport coefficients are also derived in near-equilibrium realm.

The steepest-entropy-ascent quantum thermodynamic (SEAQT) framework is used to model the decoherence\ud that occurs during the state evolution of two different microscopic composite systems. The test cases are a\ud two-spin-1/2-particle composite system and a particle-photon field composite system like that experimentally\ud studied in cavity quantum electrodynamics. The first system is used to study the characteristics of the nonlinear\ud equation of motion of the SEAQT framework when modeling the state evolution of a microscopic composite\ud system with particular interest in the phenomenon of decoherence. The second system is used to compare the\ud numerical predictions of the SEAQT framework with experimental cavity quantum electrodynamic data available\ud in the literature. For the two different numerical cases presented, the time evolution of the density operator of\ud the composite system as well as that of the reduced operators belonging to the two constituents is traced from\ud an initial nonequilibrium state of the composite along its relaxation towards stable equilibrium. Results show for\ud both cases how the initial entanglement and coherence is dissipated during the state relaxation towards a state of\ud stable equilibrium

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