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Proceedings of the National Academy of Sciences

The second law as a selection principle: The microscopic theory of dissipative processes in quantum systems

Ilya Prigogine, Cl. George

Published Jul 1, 1983• 64 citations
Publisher

Abstract

The second law of thermodynamics, for quantum systems, is formulated, on the microscopic level. As for classical systems, such a formulation is only possible when specific conditions are satisfied (continuous spectrum, nonvanishing of the collision operator, etc.). The unitary dynamical group can then be mapped into two contractive semigroups, reaching equilibrium either for t --> +infinity or for t --> -infinity. The second law appears as a symmetry-breaking selection principle, limiting the observables and density functions to the class that tends to thermodynamic equilibrium in the future (for t --> +infinity). The physical content of the dynamical structure is now displayed in terms of the appropriate semigroup, which is realized through a nonunitary transformation. The superposition principle of quantum mechanics has to be reconsidered as irreversible processes transform pure states into mixtures and unitary transformations are limited by the requirement that entropy remains invariant. In the semigroup representation, interacting fields lead to units that behave incoherently at equilibrium. Inversely, nonequilibrium constraints introduce correlations between these units.

DOI
10.1073/pnas.80.14.4590

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The second law of thermodynamics, for quantum systems, is formulated, on the microscopic level. As for classical systems, such a formulation is only possible when specific conditions are satisfied (continuous spectrum, nonvanishing of the collision operator, etc.). The unitary dynamical group can then be mapped into two contractive semigroups, reaching equilibrium either for t --> +infinity or for t --> -infinity. The second law appears as a symmetry-breaking selection principle, limiting the observables and density functions to the class that tends to thermodynamic equilibrium in the future (for t --> +infinity). The physical content of the dynamical structure is now displayed in terms of the appropriate semigroup, which is realized through a nonunitary transformation. The superposition principle of quantum mechanics has to be reconsidered as irreversible processes transform pure states into mixtures and unitary transformations are limited by the requirement that entropy remains invariant. In the semigroup representation, interacting fields lead to units that behave incoherently at equilibrium. Inversely, nonequilibrium constraints introduce correlations between these units.
Quantum mechanics is widely recognised as being incomplete. It is not consistent with the second law of thermodynamics and does not provide a scientifically credible physical account of the measurement process, the means by which coherence is broken and classically observable states are recorded. This has led to many ad hoc assumptions being used to account for various properties of quantum systems, among which is the coherence time of quantum devices that determines their ability to perform computations. Here, we show that all these properties can be accommodated naturally and consistently in the context of mixing quantum systems which exhibit continuous spectra, as arises in the thermodynamic limit in quantum statistical mechanics and quantum gravity. In particular, for isolated systems we show that the time-reversal symmetry associated with unitary time evolution of the quantum state gives rise to time-symmetry breaking and a semi-group evolution which attains thermodynamic equilibrium at long times. Moreover, the emergence of this non-unitary time-asymmetry leads to microcanonical equilibrium states in which all quantum coherence is lost and is accompanied by the transformation of pure states into mixtures, leading in turn to an increase in entropy. Inclusion of a macroscopic measurement apparatus shows how the outcome of a measurement corresponds to the von Neumann projection postulate, arising with probabilities in conformance with the Born rule. The mathematical structure of the theory which applies to quantum systems with continuous spectra is closely analogous to the classical ergodic theory of dynamical systems and the conditions under which they attain equilibrium states.
The second law of thermodynamics for adiabatic operations -- constraints on state transitions in closed systems under external control -- is one of the fundamental principles of thermodynamics. On the other hand, it is recently established that even pure quantum states can represent thermal equilibrium. However, pure quantum states do not satisfy the second law in that they are not passive, i.e., work can be extracted from them if arbitrary unitary operations are allowed. It therefore remains unresolved how quantum mechanics can be reconciled with thermodynamics. Here, based on our key quantum-mechanical notions of thermal equilibrium and adiabatic operations, we address the emergence of the second law for adiabatic operations in the thermodynamics limit. We first introduce infinite-observable macroscopic thermal equilibrium (iMATE); a quantum state, including pure states, is in iMATE if the expectation values of all additive observables agree with their equilibrium values. We also introduce a macroscopic operation as unitary evolution generated by a time-dependent additive Hamiltonian, which is regarded as corresponding to adiabatic operations. Employing these concepts, we show that no extensive work can be extracted from any quantum state in iMATE through any macroscopic operations. Furthermore, we introduce a quantum-mechanical form of entropy density such that it agrees with thermodynamic entropy density for any quantum state in iMATE. We then prove that for any initial state in iMATE, this entropy density cannot be decreased by any macroscopic operations, followed by a time-independent relaxation process. Our theory thus proves two different forms of the second law, by adopting macroscopically reasonable classes of observables, equilibrium states, and operations. We also discuss the time scales of macroscopic operations in these results.
The microscopic theory of irreversible processes that we developed is summarized and illustrated, using as a simple example the Friedrichs model. Our approach combines the Poincaré's point of view (dynamical interpretation of irreversibility) with the Gibbs-Einstein ensemble point of view. It essentially consists in a nonunitary transformation theory based on the symmetry properties of the Liouville equation and dealing with continuous spectrum. The second law acquires a microscopic content in terms of a Liapounov function which is a quadratic functional of the density operator. In our new representation of dynamics, which is defined for a restricted set of observables and states, this functional takes a universal form. We obtain, in this way, a semi-group description, the generator of which contains a part directly related to the microscopic entropy production. The Friedrichs model gives us a simple field theoretical example for which the entropy production can be evaluated. The thermodynamical meaning of life-times is explicitly displayed. The transition from pure states to mixtures, as well as the occurrence of long tails in thermodynamic systems, are also briefly discussed.
The compatibility of irreversibility, as expressed by the second law of thermodynamics, with ordinary quantum mechanics is a challenging problem. Our solution requires an extension of the latter. Such an extension of a reversible formalism is made possible by the presence of self‐energy processes (already found in quantum electrodynamics) which enables the widening of the dynamics by the introduction of specific additionnal variables leading to the recognition of such processes. A projection technique modeled on the one introduced long ago by the Brussels group defines a subdynamics which is shown to contain entirely the starting formulation (it corresponds now to a restricted class of initial conditions, namely the reversible one). A new kinetic description is obtained in which e.g. collision processes for privileged components arise from the original interaction. This method is applied successively to various models and we focus in this paper on the possible presence of temporal behaviours excluded in ordinary quantum mechanics. Among those differences, the possibility appears of a purely exponential decay for a particle while ordinary quantum mechanics requires long time tails associated with the finite lower bound in the spectrum of the Hamiltonian.
We construct a macroscopic thermodynamical theory that satisfies the second law of thermodynamics, based on quantum mechanics. More concretely, our macroscopic theory satisfies the following two features: (1) A macroscopic equilibrium state is expressed as a set of macroscopic variables a⃗=(a1,⋯ ,aL)\vec{a}=(a_1,\cdots,a_L)a=(a1​,⋯,aL​), which represents coarse-grained values of a set of physical quantities, and (2) An adiabatic transformation from an equilibrium state a⃗\vec{a}a to another state a⃗′\vec{a}'a′ is possible if and only if sa⃗≤sa⃗′s_{\vec{a}}\le s_{\vec{a}'}sa​≤sa′​ holds. Here, sa⃗s_{\vec{a}}sa​ is a real-valued function corresponding to the thermodynamical entropy, which depends only on macroscopic variables a⃗\vec{a}a. We show that such a macroscopic thermodynamical theory can be consistently constructed if the von-Neumann entropy of a generalized microcanonical state satisfies a generalized central limit theorem. We also show that even when the von-Neumann entropies do not satisfy the condition, a macroscopic thermodynamic-like theory with a similar structure exists, which could be at the foundations of nonequilibrium thermodynamics. Finally, we make a replica of (U,V,N)(U,V,N)(U,V,N) expression of thermodynamics satisfying (1) and (2), using a toy model of free particles in a box.
It is difficult to incorporate the concept of interacting physical particles in the frame of conventional quantum mechanics. It comes from the fact that in this formalism the Hamiltonian plays a dual role as the generator of motion and as the observable associated with the energy. As a result it is easy to define either a representation in which particles interact but are not well defined (a representation in which the Hamiltonian is not diagonal) or a representation in which the units are well defined but do not interact. We expect that in the search for a representation in which we may speak of both well defined and still interacting particles, the distinction between reversible and irreversible processes should play a basic role. Certainly we do not want to eliminate irreversible processes such as scattering, production or decay which are basically related to the mechanisms through which we observe particles. To distinguish between reversible and irreversible processes we have to work in a representation such that a Liapounov function (the entropy) may be ascribed to the time evolution of the system. The introduction of such a representation through a specific class of non-unitary transforms is described. We then propose newmore » quantum rules directly applicable to dissipative systems with a Liapounov function. For systems with a discrete spectrum these new quantum rules reduce trivially to the usual quantum rules as formulated by Born, Jordan and Heisenberg. The theory is applied to a simple field theoretical model - the so-called Friedrichs model-for which all calculations can be performed exactly.« less