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The second law of thermodynamics requires concave energy function of coupling constant in classical and quantum dynamics

Chigak Itoi, M. Amano

Published Nov 5, 2019• 0 citations
OpenAlex

Abstract

Quantum dynamics controlled by a time-dependent coupling constant are studied. It is proven that an energy eigenstate expectation value of work done by the system in a quench process cannot exceed the work in the corresponding quasi-static process, if and only if the energy eigenvalue is a concave function of the coupling constant. We propose this concavity of energy eigenvalues as a new universal criterion for quantum dynamical systems to satisfy the second law of thermodynamics. We argue simple universal conditions on quantum systems for the concavity, and show that every energy eigenvalue is indeed concave in some specific quantum systems. These results agree with the maximal work principle for adiabatic quench and quasi-static processes as an expression of the second law of thermodynamics. Our result gives a simple example of an integrable system satisfying an analogue to the strong eigenstate thermalization hypothesis (ETH) with respect to the principle of maximum work.

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Quantum dynamics controlled by a time-dependent coupling constant are studied. It is proven that an energy eigenstate expectation value of work done by the system in a quench process cannot exceed the work in the corresponding quasi-static process, if and only if the energy eigenvalue is a concave function of the coupling constant. We propose this concavity of energy eigenvalues as a new universal criterion for quantum dynamical systems to satisfy the second law of thermodynamics. We argue simple universal conditions on quantum systems for the concavity, and show that every energy eigenvalue is indeed concave in some specific quantum systems. These results agree with the maximal work principle for adiabatic quench and quasi-static processes as an expression of the second law of thermodynamics. Our result gives a simple example of an integrable system satisfying an analogue to the strong eigenstate thermalization hypothesis (ETH) with respect to the principle of maximum work.
Quantum dynamics controlled by a time-dependent coupling constant are studied. It is proven that an energy eigenstate expectation value of work done by the system in a quench process cannot exceed the work in the corresponding quasi-static process, if and only if the energy eigenvalue is a concave function of the coupling constant. We propose this concavity of energy eigenvalues as a new universal criterion for quantum dynamical systems to satisfy the second law of thermodynamics. We argue simple universal conditions on quantum systems for the concavity, and show that every energy eigenvalue is indeed concave in some specific quantum systems. These results agree with the maximal work principle for adiabatic quench and quasi-static processes as an expression of the second law of thermodynamics. Our result gives a simple example of an integrable system satisfying an analogue to the strong eigenstate thermalization hypothesis (ETH) with respect to the principle of maximum work.
A recently proposed quantum mechanical criterion `concavity of energy' for the second law of thermodynamics is studied also for classical particle systems confined in a bounded region by a potential with a time-dependent coupling constant. It is shown that the time average of work done by particles in a quench process cannot exceed that in the corresponding quasi-static process, if the energy is a concave function of the coupling constant. It is proven that the energy is indeed concave for a general confining potential with certain properties. This result implies that the system satisfies the principle of maximum work in the adiabatic environment as an expression of the second law of thermodynamics.
Work extraction from the Gibbs ensemble by a cyclic operation is impossible, as represented by the second law of thermodynamics. On the other hand, the eigenstate thermalization hypothesis (ETH) states that just a single energy eigenstate can describe a thermal equilibrium state. Here, we attempt to unify these two perspectives and investigate the second law at the level of individual energy eigenstates, by examining the possibility of extracting work from a single energy eigenstate. Specifically, we performed numerical exact diagonalization of a quench protocol of local Hamiltonians and evaluated the number of work-extractable energy eigenstates. We found that it becomes exactly zero in a finite system size, implying that a positive amount of work cannot be extracted from any energy eigenstate, if one or both of the prequench and the postquench Hamiltonians are nonintegrable. We argue that the mechanism behind this numerical observation is based on the ETH for a nonlocal observable. Our result implies that quantum chaos, characterized by nonintegrability, leads to a stronger version of the second law than the conventional formulation based on the statistical ensembles.
We show that the maximum extractable work (ergotropy) from a quantum many-body system is constrained by "local athermality" of an initial state and "local entropy decrease" brought about by quantum operations. The obtained universal upper bound on ergotropy implies that the eigenstate thermalization hypothesis prohibits work extraction from energy eigenstates by means of finite-time unitary operations. This no-go property implies that Planck's principle, a form of the second law of thermodynamics, holds even for pure quantum states. Our result bridges two independently studied concepts of quantum thermodynamics, the second law and thermalization, via "intrasystem" correlations in many-body systems as a resource for work extraction.
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.
Under the eigenstate thermalization hypothesis (ETH), quantum-quenched systems equilibrate towards canonical, thermal ensembles. While at first glance the ETH might seem a very strong hypothesis, we show that it is indeed not only sufficient but also necessary for thermalization. More specifically, we consider systems coupled to baths with well-defined macroscopic temperature and show that whenever all product states thermalize then the ETH must hold. Our result definitively settles the question of determining whether a quantum system has a thermal behavior, reducing it to checking whether its Hamiltonian satisfies the ETH.