Building on parallels between geometric quantum mechanics and classical mechanics, we explore an alternative basis for quantum thermodynamics that exploits the differential geometry of the underlying state space. We focus on microcanonical and canonical ensembles, looking at the geometric counterpart of Gibbs ensembles for distributions on the space of quantum states. We show that one can define quantum heat and work in an intrinsic way, including single-trajectory work. We reformulate thermodynamic entropy in a way that accords with classical, quantum, and information-theoretic entropies. We give both the first and second laws of thermodynamics and Jarzynki's fluctuation theorem. Overall, this results in a more transparent physics than conventionally available. The mathematical structure and physical intuitions underlying classical and quantum dynamics are seen to be closely aligned. The experimental relevance is brought out via a stochastic model for chiral molecules (in the two-state approximation) and Josephson junctions. Numerically, we demonstrate this invariably leads to the emergence of the geometric canonical ensemble.
Building on parallels between geometric quantum mechanics and classical mechanics, we explore an alternative basis for quantum thermodynamics that exploits the differential geometry of the underlying state space. We focus on microcanonical and canonical ensembles, looking at the geometric counterpart of Gibbs ensembles for distributions on the space of quantum states. We show that one can define quantum heat and work in an intrinsic way, including single-trajectory work. We reformulate thermodynamic entropy in a way that accords with classical, quantum, and information-theoretic entropies. We give both the first and second laws of thermodynamics and Jarzynki's fluctuation theorem. Overall, this results in a more transparent physics than conventionally available. The mathematical structure and physical intuitions underlying classical and quantum dynamics are seen to be closely aligned. The experimental relevance is brought out via a stochastic model for chiral molecules (in the two-state approximation) and Josephson junctions. Numerically, we demonstrate this invariably leads to the emergence of the geometric canonical ensemble.
We formulate a geometric framework in which physical laws emerge from restricted access to microscopic information. Measurement constraints are modeled as a gauge symmetry acting on density operators, inducing a gauge-reduced space of physically distinguishable states. In the case of quantum thermodynamics, this construction leads to a gauge-invariant formulation in which the invariant entropy admits a stochastic description and satisfies a general detailed fluctuation theorem. From this result, we derive an integrated fluctuation theorem and a Clausius-like inequality that unifies the first and second laws in terms of invariant work and coherent heat. Entropy production is identified with the relative entropy between forward and backward probability measures on the gauge-reduced space of thermodynamic trajectories, revealing irreversibility as a geometric consequence of limited observability. The third law emerges as a singular zero-temperature limit in which thermodynamic orbits collapse and entropy production vanishes. Since the framework applies to arbitrary information constraints, it encompasses energy-based thermodynamics as a particular case of more general measurement scenarios.
Classical and quantum statistical mechanics are cast here in the language of projective geometry to provide a unified geometrical framework for statistical physics. After reviewing the Hilbert–space formulation of classical statistical thermodynamics, we show that the specification of a canonical polarity on the real projective space RPn induces a Riemannian metric on the state space of statistical mechanics. In the case of the canonical ensemble, equilibrium thermal states are determined by a Hamiltonian gradient flow with respect to this metric. This flow is characterized by the property that it induces a projective automorphism on the state manifold. The measurement problem for thermal systems is studied by the introduction of the concept of a random state. The general methodology is then extended to establish a new framework for the quantum–mechanical dynamics of equilibrium thermal states. In this case, the relevant phase space is the complex projective space CPn, here regarded as a real manifold γ endowed with the Fubini–Study metric and a compatible symplectic structure. A distinguishing feature of quantum thermal dynamics is the inherent multiplicity of thermal trajectories in the state space, associated with the non–uniqueness of the infinite–temperature state. We are then led to formulate a geometric characterization of the standard KMS relation often considered in the context of C* algebras. Finally, we develop a theory of the quantum microcanonical and canonical ensembles, based on the geometry of the quantum phase space γ. The example of a particle of quantum spin–1/2 particle in a heat bath is studied in detail.
Recently, the possibility of investigating single molecule, or single spin observables, as well as the necessity of a better understanding of the mechanisms underlying quantum dynamics in order to obtain nanoscale devices and nanostructered materials suitable for quantum computing tasks, have revived the interest in foundational aspects of quantum statistical mechanics. This thesis aims to give a contribution to this field by re-considering the statistical characterization of a quantum system at the light of some paradigmatic changes in our understanding of quantum theory which have taken place in the last two decades. In particular the impressive development of quantum information theory has changed the perceptions of quantum entanglement: for a long time it has been considered a somewhat paradoxical property of the matter at the atomic scale, but now it is regarded as an essential and ubiquitous phenomenon whose consequences are affecting the very macroscopic world that we experience. Still the decoherence program has brought out the importance of considering a quantum system together with its environment in order to clarify some key aspects of quantum dynamics. Thus, we start from the idea that quantum correlations are ubiquitous and somewhat uncontrollable in systems with many degrees of freedom which are typically considered in statistical mechanics. As a consequence we assume the standpoint that quantum statistical mechanics has not to be based on the underlying idea of a collection of many, independent quantum systems but rather it has to emerge at the level of a global wavefunction (pure state) which describes the system as well as its environment as a whole. In order to investigate the consequences of these assumptions we study the equilibrium distribution of an isolated quantum system. This is defined, in analogy with the ergodic foundations of classical statistical mechanics, on the basis of the time evolution of the quantum state. Then, we study the emergence of thermodynamic properties in a quantum system by studying the probability distribution of some function of interests, as the entropy and the equilibrium state of a subsystem, on Ensembles of Pure States. Such a probability distribution is derived from the geometry of the Hilbert space, and the theoretical tools suitable for its characterization are developed. On the one hand we perform a numerical sampling of the ensemble distributions by employing Monte Carlo techniques, on the other hand simpler analytical approximation of the geometrical distributions are derived by means of a maximum entropy principle. Model systems composed of an ensemble of spins are chosen to illustrate the salient features which emerge from the developed theoretical framework: the main point is that the Ensemble Distributions of “thermodynamic observables” (entropy or equilibrium state of a subsystem) are sharply peaked around a typical value. From the analysis it emerges that each of the overwhelming majority of the wavefunctions which has appreciable weight in the considered ensemble, is characterized by the same value of the “macroscopic” functions. This is a striking evidence of the “typicality” of these properties. In the essence, our impossibility to know the state of the system in detail does not matter, just for the remarkable fact that almost all quantum states behave essentially in the same way. By virtue of this typicality the study of the behaviour of the typical values of the thermodynamic function become meaningful. Notably, under certain conditions, one recovers the results of standard statistical mechanics, that is, the equilibrium average of the state of a subsystem can be cast in the Boltzmann canonical form at the temperature given by the usual thermodynamical relation . In the second part of the thesis we consider the dynamical aspects of the equilibrium state of a subsystem interacting with its environment. The fluctuations around the equilibrium average critically depends on the entanglement between the system and the environment and on the form of the interaction Hamiltonian. The connection between the dynamics of the fluctuations of an observable at the equilibrium and the relaxation toward the equilibrium from a “non typical” initial value is also investigated with the aid of simple model systems. The study presented in this thesis was partly motivated by a critical analysis of the statistical methods available for the theoretical modelling of magnetic resonance experiments. One of these, the Stochastic Liouville Equation, has been employed in a work completed during the first year of my Ph.D. program in order to interpret some feature of a two dimensional electron spin resonance experiment, [Fresch B., Frezzato D., Moro G. J., Kothe G., Freed J. H.; J. Phys. Chem. B., 110, 24238, (2006)].
To understand in detail the relation between unitary quantum theory that describes our world at the microscopic scale and thermodynamics, which was long believed only to apply to macroscopic objects, is one of the most interesting and long-standing problems in physics. Recently, this problem has received renewed attention, in particular from the community of quantum information theory, but also from the field of statistical mechanics, inspired from stochastic thermodynamics. These results suggest that thermodynamics is also relevant for individual quantum systems, provided that they can be brought into contact with thermal baths. In this thesis, I use recently developed tools to provide new results both on fundamental questions, but also on questions which are of practical relevance for potential miniaturized thermal machines. In terms of fundamental questions, the results in this thesis contribute to understanding how the basic laws of thermodynamics and statistical mechanics can be understood directly from unitary quantum mechanics. In particular, I discuss and answer the following questions: i) How can we quantify the third law of thermodynamics using information theoretic methods? ii) How can we quantify the "thermodynamic value" of a state-transition in quantum systems? iii) How can we axiomatically characterize the non-equilibrium free energy and relative entropy? iv) How can we justify statistical ensembles from an operational perspective, without having to introduce either some probability measures or an information theoretic entropy measure? v) How can we understand the equilibration of closed quantum systems, how long does it take and how difficult is it to avoid? In the second part of the thesis I discuss in detail how experimental restrictions, which become important at the quantum scale, influence the ultimate thermodynamic bounds for thermal machines. In particular, the results in this thesis provide thermodynamic bounds on work-extraction and efficiencies of thermal machines in situations where 1.) an experimenter only has limited field strengths available, 2.) an experimenter cannot control the interactions between particles, but external fields arbitrarily well, and 3.) situations in which a small quantum system can only be strongly coupled to heat baths. These bounds are tight and I provide explicit examples illustrating the different behaviours. Finally, I come back to a classic problem in statistical physics: The emergence of spontaneous symmetry breaking. Here, I provide general and rigorous new results that show how symmetry-breaking stationary states emerge from fluctuations in order parameters in dissipative lattice models.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
Classical and quantum statistical mechanics are cast here in the language of projective geometry to provide a unified geometrical framework for statistical physics. After reviewing the Hilbert space formulation of classical statistical thermodynamics, we introduce projective geometry as a basis for analysing probabilistic aspects of statistical physics. In particular, the specification of a canonical polarity on RPn induces a Riemannian metric on the state space of statistical mechanics. In the case of the canonical ensemble, we show that equilibrium thermal states are determined by the Hamiltonian gradient flow with respect to this metric. This flow is concisely characterised by the fact that it induces a projective automorphism on the state manifold. The measurement problem for thermal systems is studied by the introduction of the concept of a random state. The general methodology is then extended to include the quantum mechanical dynamics of equilibrium thermal states. In this case the relevant state space is complex projective space, here regarded as a real manifold endowed with the natural Fubini-Study metric. A distinguishing feature of quantum thermal dynamics is the inherent multiplicity of thermal trajectories in the state space, associated with the nonuniqueness of the infinite temperature state. We are then led to formulate a geometric characterisation of the standard KMS-relation often considered in the context of C∗-algebras. The example of a quantum spin one-half particle in heat bath is studied in detail.