No Arabic abstract
We develop the stochastic approach to thermodynamics based on the stochastic dynamics, which can be discrete (master equation) continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second, the definition of entropy production rate which is nonnegative and vanishes in thermodynamic equilibrium. Based on these assumptions we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium, and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasi-equilibrium processes, the convexity of the equilibrium surface, the monotonic time behavior of thermodynamic potentials, including entropy, the bilinear form of the entropy production rate, the Onsager coefficients and reciprocal relations, and the nonequilibrium steady states of chemical reactions.
This work presents a unified dissipaton-equation-of-motion (DEOM) theory and its evaluations on the Helmholtz free energy change due to the isotherm mixing of two isolated subsystems. One is a local impurity and another is a nonlocal Gaussian bath. DEOM constitutes a fundamental theory for such open quantum mixtures. To complete the theory, we construct also the imaginary-time DEOM formalism via an analytical continuation of dissipaton algebra, which would be limited to equilibrium thermodynamics. On the other hand, the real-time DEOM deals with both equilibrium structural and nonequilibrium dynamic properties. Its combination with the thermodynamic integral formalism would be a viable and accurate means to both equilibrium and transient thermodynamics. As illustrations, we report the numerical results on a spin--boson system, with elaborations on the underlying anharmonic features, the thermodynamic entropy versus the von Neumann entropy, and an indication of solvent-cage formation. Beside the required asymptotic equilibrium properties, the proposed transient thermodynamics also supports the basic spontaneity criterion.
The total entropy production of stochastic systems can be divided into three quantities. The first corresponds to the excess heat, whilst the second two comprise the house-keeping heat. We denote these two components the transient and generalised house-keeping heat and we obtain an integral fluctuation theorem for the latter, valid for all Markovian stochastic dynamics. A previously reported formalism is obtained when the stationary probability distribution is symmetric for all variables that are odd under time reversal which restricts consideration of directional variables such as velocity.
We present the closed loop approach to linear nonequilibrium thermodynamics considering a generic heat engine dissipatively connected to two temperature baths. The system is usually quite generally characterized by two parameters: the output power $P$ and the conversion efficiency $eta$, to which we add a third one, the working frequency $omega$. We establish that a detailed understanding of the effects of the dissipative coupling on the energy conversion process, necessitates the knowledge of only two quantities: the systems feedback factor $beta$ and its open-loop gain $A_{0}$, the product of which, $A_{0}beta$, characterizes the interplay between the efficiency, the output power and the operating rate of the system. By placing thermodynamics analysis on a higher level of abstraction, the feedback loop approach provides a versatile and economical, hence a very efficient, tool for the study of emph{any} conversion engine operation for which a feedback factor may be defined.
In stochastic thermodynamics standard concepts from macroscopic thermodynamics, such as heat, work, and entropy production, are generalized to small fluctuating systems by defining them on a trajectory-wise level. In Langevin systems with continuous state-space such definitions involve stochastic integrals along system trajectories, whose specific values depend on the discretization rule used to evaluate them (i.e. the interpretation of the noise terms in the integral). Via a systematic mathematical investigation of this apparent dilemma, we corroborate the widely used standard interpretation of heat- and work-like functionals as Stratonovich integrals. We furthermore recapitulate the anomalies that are known to occur for entropy production in the presence of temperature gradients.
The theory of large deviations has been applied successfully in the last 30 years or so to study the properties of equilibrium systems and to put the foundations of equilibrium statistical mechanics on a clearer and more rigorous footing. A similar approach has been followed more recently for nonequilibrium systems, especially in the context of interacting particle systems. We review here the basis of this approach, emphasizing the similarities and differences that exist between the application of large deviation theory for studying equilibrium systems on the one hand and nonequilibrium systems on the other. Of particular importance are the notions of macroscopic, hydrodynamic, and long-time limits, which are analogues of the equilibrium thermodynamic limit, and the notion of statistical ensembles which can be generalized to nonequilibrium systems. For the purpose of illustrating our discussion, we focus on applications to Markov processes, in particular to simple random walks.