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 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 second law of thermodynamics states that the entropy of an isolated system can only increase over time. This appears to conflict with the reversible evolution of isolated quantum systems under the Schrödinger equation, which preserves the von Neumann entropy. Nonetheless, one finds that with respect to many observables, expectation values approach a fixed value—their equilibrium value. This ultimately raises the question: ? For classical systems, one introduces the assumption of a low-entropy initial state along with the concept of ignorance about the microscopic details of the physical system, leading to a statistical interpretation of the second law. By considering the observables through which we examine quantum systems, both these assumptions can be incorporated, building upon recent studies of the of observables. While the statistical behavior of observable expectation values is well established, a quantitative connection to entropy increase has been lacking so far. In deriving novel bounds for the equilibration of observables, and considering the entropy of the system relative to observables, we recover a variant of the second law: the entropy with respect to a given observable tends toward its equilibrium value in the course of the system’s unitary evolution. These results also support recent findings that question the necessity of nonintegrability for equilibration in quantum systems. We further illustrate our bounds using numerical results from the paradigmatic example of a quantum Ising model on a chain of spins. There, we observe entropy increasing up to equilibrium values, as well as fluctuations, which expose the underlying reversible evolution in accordance with the derived bounds.
We build a framework for the thermodynamics of macroscopic quantum systems. In contrast with approaches requiring access to the full density matrix, our framework relies on a coarse-grained description, based on measurement statistics of a few observables. When these observables commute, the outcomes define classical macrostates whose entropy is quantified by observational entropy, accounting for uncertainty about both the macrostate and the microstate within it. We extend this notion to non-commuting observables forming a subalgebra of the operator space, and use Jaynes' principle to define an algebra-dependent entropy interpolating between von Neumann and observational entropies. Given initial and final measurement sets, connected by internal and/or environment-induced dynamics, we derive a second law for the coarse-grained dynamics. Unlike formulations based on von Neumann entropy, our inequality captures irreversibility from both non-unitary environment-induced dynamics and internal equilibration. It takes the usual form of a positive entropy production when the system is initially at internal equilibrium, while correction terms capture nonequilibrium resources ignored by the coarse-graining. We also derive fluctuation theorems for coarse-grained thermodynamic quantities. Along a quasi-static path of measurement schemes, we identify quantum macroscopic notions of work and heat fulfilling the first and second laws, including an additional work contribution from manipulating the algebra to which the system is confined, through external constraints or quantum measurement backaction. Finally, we apply our framework to examples illustrating the impact of varying the coarse-graining scheme. Our approach unifies macroscopic and stochastic thermodynamics in a genuinely quantum framework, laying the basis for a versatile, experimentally friendly toolbox to analyze complex quantum dynamics.
We improve on our version of the second law of thermodynamics as a deterministic theorem for quantum spin systems [ 1 ] in two basic aspects. The first concerns the general statement of the second law: spontaneous changes in an adiabatically closed system will always be in the direction of increasing (mean) entropy, which rises to a maximal value. In order to arrive at this statement, we have to extend the previous definition of adiabatic transformation, in order to include sudden interactions, and thereby generalize the “barrier model”. The cornerstone of the second law is then seen to be the fact that the dynamics may induce a basic structural transition between states of infinite systems in the limit of large times, which, physically, represent times much larger than specific relaxation times. Two specific examples concern the transition from pure to mixed states in two different universality classes of dynamics in one dimension, one being the exponential model, which has exactly soluble dynamics and does not display a phase transition, the other the Dyson model(s), for which neither the dynamics nor the statistical mechanics are exactly soluble, and which do exhibit a (ferromagnetic) phase transition, first demonstrated by Dyson. It is also shown, as a consequence of results of Albert and Kiessling on the Cloitre function, that there is strong graphical evidence that the dynamics of the Dyson models are chaotic for large times, and, thereby, that the mechanisms of approach to equilibrium differ for these two universality classes in a profound way, which depend exclusively on the dynamics, and not on the states and observables.
Recent theoretical and experimental work on the foundations of statistical mechanics and thermodynamics has shown that quantum pure states typically evolve to thermal equilibrium. We focus on formulating the second law of thermodynamics for these states. The standard quantum von Neumann quantum entropy is constant during equilibration, S^{vN}=0, in apparent conflict with the entropy increase of the second law, ΔS_{univ} > 0. We explore a recently developed entropy S_{univ}^Q for a pure state and test its behavior in simulations of a model system and environment evolving in time with heat flow to equilibrium. We find that the entropy approaches the correct classical value in a type of classical limit with weak coupling. With stronger coupling, we find a new source of quantum "excess entropy production," which has its origin in the quantum spreading of the wavepacket. Are there quantum thermodynamic effects related to this new source of entropy? To test this, we developed a model for a small variable temperature quantum oscillator bath. We performed simulations where two small baths are linked by a system, with unequal couplings to the baths. The model evolves to a novel type of equilibrium state with unequal temperatures in the baths, with heat flow from cold to hot along the path to equilibrium. We give an account of this behavior in terms of the second law with the quantum entropy S_{univ}^Q. The new formulation of the second law thus appears well-founded and fruitful, with surprising new quantum thermodynamic effects that may still be awaiting discovery, for example in molecules or systems far from equilibrium. \n\nThis dissertation includes previously published and unpublished co-authored material.
Thermodynamics is commonly presented as a theory of macroscopic systems in stable equilibrium, built upon assumptions of extensivity and scaling with system size. In this paper, we present a universal formulation of the elementary foundations of thermodynamics, in which entropy and energy are defined and employed beyond equilibrium and without assuming extensivity. The formulation applies to all systems -- large and small, with many or few particles -- and to all states, whether equilibrium or nonequilibrium, by relying on carefully stated operational definitions and existence principles rather than macroscopic idealizations. Key thermodynamic concepts, including adiabatic availability and available energy, are developed and illustrated using the energy-entropy diagram representation of nonequilibrium states, which provides geometric insight into irreversibility and the limits of work extraction for systems of any size. A substantial part of the paper is devoted to the analysis of entropy transfer in non-work interactions, leading to precise definitions of heat interactions and heat-and-diffusion interactions of central importance in mesoscopic continuum theories of nonequilibrium behavior in simple and complex solids and fluids. As a direct consequence of this analysis, Clausius inequalities and the Clausius statement of the second law are derived in forms explicitly extended to nonequilibrium processes. The resulting framework presents thermodynamics as a universal theory whose concepts apply uniformly to all systems, large and small, and provides a coherent foundation for both teaching and modern applications.
The irreversible entropy increase described by the second law of thermodynamics is fundamentally tied to thermalization and the emergence of equilibrium. In the first part of our work (Ref: arXiv.2503.04152), we constructed an isolated gas system model and numerically demonstrated irreversible growth of entanglement entropy caused by erasure of spread non-equilibrium state information. Here, we mathematically prove that for a typical macroscopic system in a non-equilibrium state ∣ϕ0⟩, the quantum state ∣ϕ0′⟩=O^(t)∣ϕ0⟩ will inevitably evolve toward equilibrium. Our work demonstrates that the second law of thermodynamics, and consequently the ergodic hypothesis in statistical physics, can be understood and proven from a quantum information perspective. From this perspective, the second law can be stated as: In typical macroscopic physical systems, the spreading and erasure of non-equilibrium information is inevitable.