Equilibrium thermodynamics emerges because a vast number of microscopic states become indistinguishable at the level of local observables. We start from the observation that a nonequilibrium quantum state can also be represented by an ensemble of pure states that minimizes the average energy variance. We show that varying the statistical weights within this optimal family organizes state space into ``minimum-variance leaves'', which generalize the space of stationary states underlying equilibrium. We observe thermodynamic compression on the leaves, which in the simplest scenario manifests itself in the indistinguishability of states with the same energy density. We call this ``leaf typicality''; at equilibrium it reduces to eigenstate thermalization or its generalizations. Numerical tests support leaf typicality on some leaves and indicate a breakdown of its stronger forms on others, suggesting a rich thermodynamic organization beyond equilibrium. These results open a route to a unified statistical mechanics of equilibrium and nonequilibrium quantum states.
Equilibrium thermodynamics emerges because a vast number of microscopic states become indistinguishable at the level of local observables. We start from the observation that a nonequilibrium quantum state can also be represented by an ensemble of pure states that minimizes the average energy variance. We show that varying the statistical weights within this optimal family organizes state space into minimum-variance leaves'', which generalize the space of stationary states underlying equilibrium. We observe thermodynamic compression on the leaves, which in the simplest scenario manifests itself in the indistinguishability of states with the same energy density. We call this leaf typicality''; at equilibrium it reduces to eigenstate thermalization or its generalizations. Numerical tests support leaf typicality on some leaves and indicate a breakdown of its stronger forms on others, suggesting a rich thermodynamic organization beyond equilibrium. These results open a route to a unified statistical mechanics of equilibrium and nonequilibrium quantum states.
A central open question in quantum thermodynamics is the identification of thermodynamic entropy away from equilibrium. Although thermodynamic entropy coincides with the von Neumann entropy for a Gibbs state at equilibrium, the thermodynamic role of quantum coherence generated during nonequilibrium evolution remains unclear. Here, we show that von Neumann entropy does not, in general, represent the thermodynamic entropy governing heat exchange in coherent nonequilibrium quantum systems. By integrating the resource theory of quantum coherence with thermodynamic principles, we develop a general framework for nonequilibrium quantum thermodynamics. We identify thermodynamic entropy with the energy entropy derived from energy-measurement statistics and introduce a dynamical temperature extending the equilibrium concept to nonequilibrium states. Consequently, we obtain an exact entropy-balance relation separating the entropy flux associated with heat exchange from the coherence-loss contribution to entropy production, establishing an operational connection between quantum coherence, heat flow, and total entropy change. Unlike approaches relying on equilibrium reference states or stationary Gibbs ensembles, our framework uses instantaneous dynamical quantities and remains valid throughout transient nonequilibrium evolution. It provides consistent dynamical definitions of temperature, work, heat, and free energy. Applying the formalism to an exactly solvable open quantum system, we show that the first and second laws hold throughout transient evolution and that equilibrium thermodynamics emerges dynamically in the weak-coupling long-time limit. Our results establish a unified framework for coherent nonequilibrium quantum thermodynamics and suggest opportunities for controlling heat dissipation through coherence engineering in quantum thermal technologies.
Despite early developments on the foundations of quantum mechanics concern the wave function, quantum statistics has been developed with the density matrix formalism, leading to very important results in explaining molecular observations. Only recently, several authors argued a new interpretation by focusing on the wave function representing the quantum state of an isolated system, showing how a single wave function can exhibit statistical properties and generate the same results expected in the standard quantum statistical framework. Starting from these results, investigation on the foundations of quantum statistical mechanics has gained recently a renewed interest. As a matter of fact, the possibility of studying single molecule properties as well as the need of a better understanding of the effect of quantum dynamics, in order to develop new nanoscaled materials suitable to quantum computing tasks, have opened new intriguing questions leading to quantum statistical approaches far from being well understood and accepted. In this framework the behaviour of a single realization of quantum systems has gained a central role in the description of molecular systems. Furthermore, in recent years, an increasing number of studies has been presented on quantum dynamics through the numerical solution of the Schrödinger equation for systems of interacting components. These studies demonstrates that Quantum Dynamics Simulations could be a practicable route. In order to study phenomena such as dissipation, relaxation and thermalization, the focus has to be moved from isolated molecules to modular systems made of mutual interacting components, with model Hamiltonians possessing a sufficiently low dimensional representation. An important issue concerns the rules to be employed for the choice of the initial quantum state for the simulation of isolated systems. As long as one considers molecular degrees of freedom interacting with a (model) environment, there are no reasons to select a particular quantum state for the overall system and, therefore, a random choice has to be performed amongst a well defined statistical ensemble of pure states. Furthermore, one would like to operate a choice assuring that the simulation of the system is in a well defined thermal state with given temperature. This necessarily calls for a statistical description like for classical systems. A useful parametrization of the wave function will be presented in order to highlight the most appropriate variable for the statistical analysis. In particular some of them, called phases, retain all the dynamical information whereas the others, called populations, are the constants of motion. The latter, in particular are very important because they describe the equilibrium properties strictly related to the thermodynamic description. Since the dynamics of wave function does not supply any information about populations, the definition of a probability distribution on these variables is required. Different probability distributions on populations have been proposed, only on the bases of reasonable assumptions and they validation has been performed only with a posteriori considerations. In particular Fresch and Moro have demonstrated how the agreement with thermodynamics can be employed to discriminate different probability distributions on pure states. This had led the uniform ensembles to be, up to now, the most self-consistent models for quantum pure states. However, in this thesis I will highlight a drawback of the uniform distribution ensemble that can be described as follow: if we bring into contact two systems, even through a perturbative interaction, we are not able to describe the equilibrium properties after the interaction within the uniform distribution statistics, since the uniform character is lost. It represents a severe shortcoming of the statistical ensemble from a methodological point of view, since closed systems can be always considered as the result of interaction among previously isolated systems. On the other hand this drawback introduces a further requirement of a different nature that can be used for the definition of a new statistical ensemble. In this work I intend to find and characterize a statistical ensemble for populations that overcomes the drawbacks of the uniform distribution of pure states. The invariance of the thermal state in the coupling of identical systems will be used as a guideline in the definition af a new probability distribution on populations. Such an ensemble for pure states, called Thermalization Resilient Ensemble, provides a convenient framework for treating the interactions between quantum systems, as long as the structure of the statistical distribution is preserved and the identification of thermodynamic properties is assured. In perspective it should be the privileged statistical ensemble to implement Quantum Dynamics Simulations. Once the average properties of the Thermalization Resilient Ensemble have been introduced, I will obtain a probability distribution on pure states with the use of a geometrical analysis on the Hilbert space. The surface elements of an ellipsoidal manifold will be related to the probability density on populations. As a matter of fact the explicit form of the probability distribution is a prerequisite in order to perform Quantum Dynamical Simulations. However the results obtained through the geometrical analysis cannot be easily extended to systems with unbounded energy spectrum and an alternative strategy has been developed. A scaling algorithm on the basis of the uniform statistical ensemble will be described and this allows a well defined sampling of a probability distribution with desired averages. In this framework I demonstrate the emergence of thermodynamic behavior in the limit of macroscopic systems. In the last part of the thesis I consider the dynamical features of the thermalization experiment. Two identical systems, initially at different temperature, will be brought in interaction and the analysis of the final equilibrium state will be performed for two different generic forms of the interaction Hamiltonian, highlighting how the statistical approach can be very useful in the definition of the equilibrium in complex quantum systems.
Quantum thermalization describes how closed quantum systems can effectively reach thermal equilibrium, resolving the apparent incongruity between the reversibility of Schrödinger's equation and the second law of thermodynamics. Despite its ubiquity and conceptual significance, the precise conditions that give rise to quantum thermalization are still not well understood. After nearly a century of efforts, we have yet to find a complete mathematical proof that an effective statistical description naturally emerges the underlying quantum dynamics in generic settings. Here, we prove that quantum thermalization must occur in any qubit system with local interactions under three conditions: (i) high effective temperature, (ii) translation invariance, and (iii) no perfect resonances in the energy spectrum. Specifically, we show that a typical, low-complexity pure state drawn from any ensemble with large entropy and well-defined effective temperature becomes locally indistinguishable from a Gibbs state upon unitary evolution. In this setting, our rigorous results prove the widely anticipated notion that statistical physics should be understood as an emergent phenomenon, explicitly derived from the first principles of quantum mechanics.
The project concerns the interplay among quantum mechanics, statistical mechanics and thermodynamics, in isolated quantum systems. The underlying goal is to improve our understanding of the concept of thermal equilibrium in quantum systems. First, I investigated the role played by observables and measurements in the emergence of thermal behaviour. This led to a new notion of thermal equilibrium which is specific for a given observable, rather than for the whole state of the system. The equilibrium picture that emerges is a generalization of statistical mechanics in which we are not interested in the state of the system but only in the outcome of the measurement process. I investigated how this picture relates to one of the most promising approaches for the emergence of thermal behaviour in isolated quantum systems: the Eigenstate Thermalization Hypothesis. Then, I applied the results to study some equilibrium properties of many-body localised systems. Despite the localization phenomenon, which prevents thermalization of subsystems, I was able to show that we can still use the predictions of statistical mechanics to describe the equilibrium of some observables. Moreover, the intuition developed in the process led me to propose an experimentally accessible way to unravel the interacting nature of many-body localised systems. Second, I exploited the "Concentration of Measure" phenomenon to study the macroscopic properties of the basis states of Loop Quantum Gravity. These techniques were previously used to explain why the thermal behaviour in quantum systems is such an ubiquitous phenomenon, at the macroscopic scale. I focused on the local properties, their thermodynamic behaviour and interplay with the semiclassical limit. This was motivated by the necessity to understand, from a quantum gravity perspective, how and why a classical horizon exhibits thermal properties.
The emergence of classical behavior and the origin of thermal equilibrium are two central problems in the foundations of physics. In the standard accounts, both phenomena are typically explained through interactions with an external environment: decoherence suppresses quantum interference, while coupling to a thermal bath drives relaxation toward equilibrium. Over the last decades, however, it has become clear that equilibration and thermalization can arise even in fully isolated quantum systems, in the operational sense that the expectation values of relevant observables remain close to equilibrium values for most of the time. Here, we ask whether the same intrinsic equilibration mechanism can also account for the emergence of classical behavior. Using rigorous bounds on equilibration in closed systems, we derive sufficient conditions under which a time-evolved pure state becomes, for most times, operationally indistinguishable from a classical mixture associated with a chosen physical property. We identify two complementary routes to such operational classicality: either the chosen property almost commutes with the system Hamiltonian or the observables used to probe the system lose access to the remaining coherence after equilibration. Our results show that classical behavior need not be confined to the energy basis and may emerge even when substantial coherence remains present in the equilibrium state. This establishes a direct connection between two foundational questions: the origin of thermalization in isolated quantum systems and the quantum-to-classical transition