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Journal of Physics Conference Series

Maximum entropy production rate in quantum thermodynamics

Gian Paolo Beretta

Published Jun 1, 2010• 47 citations
Publisher

Abstract

In the framework of the recent quest for well-behaved nonlinear extensions of the traditional Schrödinger-von Neumann unitary dynamics that could provide fundamental explanations of recent experimental evidence of loss of quantum coherence at the microscopic level, a recent paper [Gheorghiu-Svirschevski 2001 Phys. Rev. A 63 054102] reproposes the nonlinear equation of motion proposed by the present author [see Beretta G P 1987 Found. Phys. 17 365 and references therein] for quantum (thermo)dynamics of a single isolated indivisible constituent system, such as a single particle, qubit, qudit, spin or atomic system, or a Bose-Einstein or Fermi-Dirac field. As already proved, such nonlinear dynamics entails a fundamental unifying microscopic proof and extension of Onsager's reciprocity and Callen's fluctuation-dissipation relations to all nonequilibrium states, close and far from thermodynamic equilibrium. In this paper we propose a brief but self-contained review of the main results already proved, including the explicit geometrical construction of the equation of motion from the steepest-entropy-ascent ansatz and its exact mathematical and conceptual equivalence with the maximal-entropy-generation variational-principle formulation presented in Gheorghiu-Svirschevski S 2001 Phys. Rev. A 63 022105. Moreover, we show how it can be extended to the case of a composite system to obtain the general form of the equation of motion, consistent with the demanding requirements of strong separability and of compatibility with general thermodynamics principles. The irreversible term in the equation of motion describes the spontaneous attraction of the state operator in the direction of steepest entropy ascent, thus implementing the maximum entropy production principle in quantum theory. The time rate at which the path of steepest entropy ascent is followed has so far been left unspecified. As a step towards the identification of such rate, here we propose a possible, well-behaved and intriguing, general closure of the dynamics, compatible with the nontrivial requirements of strong separability. Based on the time–energy Heisenberg uncertainty relation, we derive a lower bound to the internal-relaxation-time functionals that determine the rate of entropy generation. This bound entails an upper bound to the rate of entropy generation. By this extreme maximal-entropy-generation-rate ansatz, each indivisible subsystem follows the direction of steepest locally perceived entropy ascent at the highest rate compatible with the time– energy uncertainty principle.

DOI
10.1088/1742-6596/237/1/012004

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In the framework of the recent quest for well-behaved nonlinear extensions of the traditional Schrödinger-von Neumann unitary dynamics that could provide fundamental explanations of recent experimental evidence of loss of quantum coherence at the microscopic level, a recent paper [Gheorghiu-Svirschevski 2001 Phys. Rev. A 63 054102] reproposes the nonlinear equation of motion proposed by the present author [see Beretta G P 1987 Found. Phys. 17 365 and references therein] for quantum (thermo)dynamics of a single isolated indivisible constituent system, such as a single particle, qubit, qudit, spin or atomic system, or a Bose-Einstein or Fermi-Dirac field. As already proved, such nonlinear dynamics entails a fundamental unifying microscopic proof and extension of Onsager's reciprocity and Callen's fluctuation-dissipation relations to all nonequilibrium states, close and far from thermodynamic equilibrium. In this paper we propose a brief but self-contained review of the main results already proved, including the explicit geometrical construction of the equation of motion from the steepest-entropy-ascent ansatz and its exact mathematical and conceptual equivalence with the maximal-entropy-generation variational-principle formulation presented in Gheorghiu-Svirschevski S 2001 Phys. Rev. A 63 022105. Moreover, we show how it can be extended to the case of a composite system to obtain the general form of the equation of motion, consistent with the demanding requirements of strong separability and of compatibility with general thermodynamics principles. The irreversible term in the equation of motion describes the spontaneous attraction of the state operator in the direction of steepest entropy ascent, thus implementing the maximum entropy production principle in quantum theory. The time rate at which the path of steepest entropy ascent is followed has so far been left unspecified. As a step towards the identification of such rate, here we propose a possible, well-behaved and intriguing, general closure of the dynamics, compatible with the nontrivial requirements of strong separability. Based on the time–energy Heisenberg uncertainty relation, we derive a lower bound to the internal-relaxation-time functionals that determine the rate of entropy generation. This bound entails an upper bound to the rate of entropy generation. By this extreme maximal-entropy-generation-rate ansatz, each indivisible subsystem follows the direction of steepest locally perceived entropy ascent at the highest rate compatible with the time– energy uncertainty principle.
We first discuss the geometrical construction and the main mathematical features of the maximum-entropy-production/steepest-entropyascent nonlinear evolution equation proposed long ago by this author in the framework of a fully quantum theory of irreversibility and thermodynamics for a single isolated or adiabatic particle, qubit, or qudit, and recently rediscovered by other authors. The nonlinear equation generates a dynamical group, not just a semigroup, providing a deterministic description of irreversible conservative relaxation towards equilibrium from any non-equilibrium density operator. It satisfies a very restrictive stability requirement equivalent to the Hatsopoulos-Keenan statement of the second law of thermodynamics. We then examine the form of the evolution equation we proposed to describe multipartite isolated or adiabatic systems. This hinges on novel nonlinear projections defining local operators that we interpret as “local perceptions ” of the overall system’s energy and entropy. Each component particle contributes an independent local tendency along the direction of steepest increase of the locally perceived entropy at constant locally perceived energy. It conserves both the locallyperceived energies and the overall energy, and meets strong separability and non-signaling conditions, even though the local evolutions are not independent of existing correlations. We finally show how the geometrical construction can readily lead to other thermodynamically relevant models, such as of the nonunitary isoentropic evolution needed for full extraction of a system’s adiabatic availability.
The nonlinear equation of motion that accomplishes a self-consistent unification of quantum mechanics (QM) and thermodynamics conceptually different from the (von Neumann) foundations of quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but which reduces to the same mathematics for the thermodynamic equilibrium (TE) states, and contains standard QM in that it reduces to the time-dependent Schrodinger equation for zero entropy states is discussed in full mathematical detail. By restricting the discussion to a strictly isolated system (noninteracting, disentangled and uncorrelated), we show how the theory departs from the conventional QSM/QIT rationalization of the second law of thermodynamics, which instead emerges in QT (quantum thermodynamics) as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituent particles. To achieve this, the theory assumes Trρ lnρ B −k for the physical entropy and is designed to implement two fundamental ansatzs: (1) that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated and uncorrelated system admits also states that must be described by non-idempotent density operators (nonzero entropy); (2) that for such additional states the law of causal evolution is determined by the simultaneous action of a Schrodinger-von Neumann-type Hamiltonian generator and a nonlinear dissipative generator which conserves the mean values of the energy and the number of constituent particles, and in forward time drives the density operator in the 'direction' of steepest entropy ascent (maximal entropy generation). The resulting dynamics is well defined for all non-equilibrium states, no matter how far from TE. Existence and uniqueness of solutions of the Cauchy initial value problem for all density operators implies that the equation of motion can be solved not only in forward time, to describe relaxation towards TE, but also in backward time, to reconstruct the 'ancestral' or primordial lowest entropy state or limit cycle from which the system originates. Zero entropy states as well as a well defined family of non-dissipative states evolve unitarily according to pure Hamiltonian dynamics and can be viewed as unstable limit cycles of the general nonlinear dynamics.
In this paper, we outline the main features of the nonlinear quantum evolution equation proposed by the present author. Such an equation may be used as a model of reduced subsystem dynamics to complement various historical and contemporary efforts to extend linear Markovian theories of dissipative phenomena and relaxation based on master equations, Lindblad and Langevin equations, to the nonlinear and far nonequilibrium domain. It may also be used as the fundamental dynamical principle in theories that attempt to unite mechanics and thermodynamics, such as the Hatsopoulos–Gyftopoulos unified theory which motivated the original development of this well-behaved general nonlinear equation for the evolution of the density operator capable of generating irreversible deterministic relaxation to thermodynamic equilibrium from any far nonequilibrium state even for an isolated system.
In the domain of nondissipative unitary Hamiltonian dynamics, the well-known Mandelstam–Tamm–Messiah time–energy uncertainty relation τ F Δ H ≥ ℏ / 2 provides a general lower bound to the characteristic time τ F = Δ F / | d ⟨ F ⟩ / d t | with which the mean value of a generic quantum observable F can change with respect to the width Δ F of its uncertainty distribution (square root of F fluctuations). A useful practical consequence is that in unitary dynamics the states with longer lifetimes are those with smaller energy uncertainty Δ H (square root of energy fluctuations). Here we show that when unitary evolution is complemented with a steepest-entropy-ascent model of dissipation, the resulting nonlinear master equation entails that these lower bounds get modified and depend also on the entropy uncertainty Δ S (square root of entropy fluctuations). For example, we obtain the time–energy-and–time–entropy uncertainty relation ( 2 τ F Δ H / ℏ ) 2 + ( τ F Δ S / k B τ ) 2 ≥ 1 where τ is a characteristic dissipation time functional that for each given state defines the strength of the nonunitary, steepest-entropy-ascent part of the assumed master equation. For purely dissipative dynamics this reduces to the time–entropy uncertainty relation τ F Δ S ≥ k B τ , meaning that the nonequilibrium dissipative states with longer lifetime are those with smaller entropy uncertainty Δ S .
We discuss and motivate the form of the generator of a nonlinear quantum dynamical group 'designed' so as to accomplish a unification of quantum mechanics (QM) and thermodynamics. We call this nonrelativistic theory Quantum Thermodynamics (QT). Its conceptual foundations differ from those of (von Neumann) quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but for thermodynamic equilibrium (TE) states it reduces to the same mathematics, and for zero entropy states it reduces to standard unitary QM. The nonlinear dynamical group of QT is construed so that the second law emerges as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituents. It implements two fundamental ansatzs. The first is that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated system admits also states that must be described by non-idempotent density operators (nonzero entropy). The second is that for such additional states the law of causal evolution is determined by the simultaneous action of a Schroedinger-von Neumann-type Hamiltonian generator and a nonlinear dissipative generator which conserves the mean values of the energy and the number of constituents, and (in forward time) drives any density operator, no matter how far from TE, in the 'direction' of steepest entropy ascent (maximal entropy increase). The equation of motion can be solved not only in forward time, to describe relaxation towards TE, but also backwards in time, to reconstruct the 'ancestral' or primordial lowest entropy state or limit cycle from which the system originates.
First, we briefly address the questions: “Is entropy defined for non‐equilibrium states?” and “Is entropy an intrinsic property of matter?”. Then, we focus on: “Is irreversibility an intrinsic feature of microscopic dynamics?” We answer this question by discussing the structure and main features of the nonlinear evolution equation proposed by this author to capture precisely how the essence of the Second Law of Thermodynamics could be embedded at the most fundamental level of description, i.e., the quantum level. The nonlinear equation generates a dynamical group providing a unique deterministic description of irreversible, conservative relaxation towards equilibrium from any non‐equilibrium state, following a locally constrained, steepest entropy ascent, maximal entropy generation path. The Hatsopoulos‐Keenan statement of the Second Law emerges as a general theorem about the Lyapunov stability of the equilibrium states of the proposed evolution equation. An appendix gives mathematical details and outlines other important theorems.