Equilibrium statistical ensembles commute with the Hamiltonian and thus carry no coherence in the energy eigenbasis. We develop a thermodynamic framework in which energy fluctuations can retain genuinely quantum-coherent contributions. We foliate state space into "minimum-variance leaves," defined by minimizing the average energy variance over all pure-state decompositions, with the minimum set by the quantum Fisher information. On each leaf we construct the least-biased state compatible with normalization and mean energy, defining a leaf-canonical ensemble. The Gibbs ensemble is recovered on the distinguished commuting leaf, while generic states are organized by their leaf label. This structure provides a natural setting to extend eigenstate thermalization beyond equilibrium via a "leaf typicality" hypothesis. According to that hypothesis, under unitary time evolution local observables depend only on the leaf and energy and, at all times, are reproduced by evolving a representative (pure) state drawn from the optimal ensemble.
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Equilibrium statistical ensembles commute with the Hamiltonian and thus carry no coherence in the energy eigenbasis. We develop a thermodynamic framework in which energy fluctuations can retain genuinely quantum-coherent contributions. We foliate state space into "minimum-variance leaves," defined by minimizing the average energy variance over all pure-state decompositions, with the minimum set by the quantum Fisher information. On each leaf we construct the least-biased state compatible with normalization and mean energy, defining a leaf-canonical ensemble. The Gibbs ensemble is recovered on the distinguished commuting leaf, while generic states are organized by their leaf label. This structure provides a natural setting to extend eigenstate thermalization beyond equilibrium via a "leaf typicality" hypothesis. According to that hypothesis, under unitary time evolution local observables depend only on the leaf and energy and, at all times, are reproduced by evolving a representative (pure) state drawn from the optimal ensemble.
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.
Quantum statistical mechanics can be fomulated based on a single pure quantum state.In this thesis, I establish this formulation, see the properties of such a pure quantum state, and apply the formulation to a practical application.Historically, it has been found that quantum states have robust "typicality", which is the property that almost all the realizable state give equilibrium values correctly for all "mechanical variables", such as energy and a correlation function.I generally call the pure quantum states which can represent the equilibrium state "thermal pure quantum (TPQ) state".I extend the typicality so that it is applicable to "genuine thermodynamic variables", such as entropy and temperature.I introduce many kinds of the TPQ states which include a "(grand)canonical TPQ state" , which is specified by intensive variables such as temperature, and a "microcanonical TPQ state", which is easy to generate.Owing to these results, I establish the new formulation of statistical mechanics based on the TPQ states.
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.
Schrödinger suggested that thermodynamical functions cannot be based on the gratuitous allegation that quantum-mechanical levels (typically the orthogonal eigenstates of the Hamiltonian operator) are the only allowed states for a quantum system [E. Schrödinger, Statistical Thermodynamics (Courier Dover, Mineola, 1967)]. Different authors have interpreted this statement by introducing density distributions on the space of quantum pure states with weights obtained as functions of the expectation value of the Hamiltonian of the system. In this work we focus on one of the best known of these distributions and prove that, when considered in composite quantum systems, it defines partition functions that do not factorize as products of partition functions of the noninteracting subsystems, even in the thermodynamical regime. This implies that it is not possible to define extensive thermodynamical magnitudes such as the free energy, the internal energy, or the thermodynamic entropy by using these models. Therefore, we conclude that this distribution inspired by Schrödinger's idea cannot be used to construct an appropriate quantum equilibrium thermodynamics.
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.