Thermodynamics at the nanoscale is known to differ significantly from its familiar macroscopic counterpart: The possibility of state transitions is not determined by free energy alone but by an infinite family of free-energy-like quantities; strong fluctuations (possibly of quantum origin) allow one to extract less work reliably than what is expected from computing the free-energy difference.However, these known results rely crucially on the assumption that the thermal machine is not only exactly preserved in every cycle but also kept uncorrelated from the quantum systems on which it acts.Here, we lift this restriction: We allow the machine to become correlated with the microscopic systems on which it acts while still exactly preserving its own state.Surprisingly, we show that this possibility restores the second law in its original form: Free energy alone determines the possible state transitions, and the corresponding amount of work can be invested or extracted from single systems exactly and without any fluctuations.At the same time, the work reservoir remains uncorrelated from all other systems and parts of the machine.Thus, microscopic machines can increase their efficiency via clever "correlation engineering" in a perfectly cyclic manner, which is achieved by a catalytic system that can sometimes be as small as a single qubit (though some setups require very large catalysts).Our results also solve some open mathematical problems on majorization which may lead to further applications in entanglement theory.
Thermodynamics at the nanoscale is known to differ significantly from its familiar macroscopic counterpart: The possibility of state transitions is not determined by free energy alone but by an infinite family of free-energy-like quantities; strong fluctuations (possibly of quantum origin) allow one to extract less work reliably than what is expected from computing the free-energy difference.However, these known results rely crucially on the assumption that the thermal machine is not only exactly preserved in every cycle but also kept uncorrelated from the quantum systems on which it acts.Here, we lift this restriction: We allow the machine to become correlated with the microscopic systems on which it acts while still exactly preserving its own state.Surprisingly, we show that this possibility restores the second law in its original form: Free energy alone determines the possible state transitions, and the corresponding amount of work can be invested or extracted from single systems exactly and without any fluctuations.At the same time, the work reservoir remains uncorrelated from all other systems and parts of the machine.Thus, microscopic machines can increase their efficiency via clever "correlation engineering" in a perfectly cyclic manner, which is achieved by a catalytic system that can sometimes be as small as a single qubit (though some setups require very large catalysts).Our results also solve some open mathematical problems on majorization which may lead to further applications in entanglement theory.
Thermodynamics is one of the main pillars of theoretical physics, and it has a special appeal of having wide applicability to a large variety of different physical systems. However, many assumptions in thermodynamics apply only to systems which are bulk material, i.e. consisting a large number of microscopic classical particles. Due to the advancement of designing nanoscale engines, especially in the light of devices that are used today in the processing of quantum information, is thermodynamics still applicable? Can we refine the core principles of thermodynamics to suit such nanoscale quantum systems as well? The central aim of this thesis is to construct a theory of thermodynamics that holds for nanoscale quantum systems, even those as small and simple as a single qubit. We do this by starting out from the core basics of quantum theory: unitary dynamics on closed quantum systems. We adapt a resource theoretic approach inspired by quantum information theory, which defines the quantum states and operations allowed to be used in a thermodynamic evolution. With this framework that naturally adopts the first law as an energy preserving condition, we show the refinement of both the zeroeth and second law of thermodynamics. The zeroeth law explains the physical significance of the Gibbs thermal state. On the other hand, we show that the second law sees refinement in the quantum nanoregime: instead of having the free energy as the sole quantity dictating the possibility of a thermodynamic state transition, we derive a family of generalized free energies that also constitute necessary conditions for a transition to occur. Moreover, these conditions become sufficient for states which are block-diagonal in the energy eigenbasis. In this thesis, we also brought our approach of thermodynamics to the next step: we apply our findings on the second laws, in order to analyze the maximum achievable efficiency for quantum heat engines. In classical thermodynamics, the Carnot efficiency has been long known as the theoretical maximum which does not depend on the specific structure of the thermal baths used, but only on its temperature. With the additional free energies we discover, we show that although quantum heat engines may achieve the Carnot efficiency, such an achievability is no longer independent of the Hamiltonians of the thermal baths. In other words, we find additional restrictions that surface in the study of quantum nanoscale heat engines, which are a direct consequence of the generalized second laws. This has provided us with a deeper understanding into the fundamental limitations of how efficient devices can be made in the realm of microscopic quantum systems.
The laws of thermodynamics strongly restrict the performance of thermal machines. Standard thermodynamics, initially developed for uncorrelated macroscopic systems, does not hold for microscopic systems correlated with their environments. We here derive an exact formula for the efficiency of any cyclically driven quantum engine by using generalized laws of quantum thermodynamics that account for all possible correlations between all involved parties, including initial correlations. Furthermore, we demonstrate the existence of two basic modes of engine operation: the usual thermal case, where heat is converted into work, and an athermal regime, where work is extracted from entropic resources, such as system-bath correlations. In the latter regime, the efficiency is not bounded by the usual Carnot formula. Our results provide a unified formalism to determine the efficiency of correlated microscopic quantum machines.
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.
Quantum thermodynamics investigates how robust the second law of thermodynamics serves as the unique fundamental law in the small quantum world. To tackle this problem, the quantum coherence constitutes a major difficulty of investigations, which provides severe constraints hindering the recovery of a single thermodynamic potential. Here we solve this long-standing problem of quantum information theory by revealing that the state convertibility under thermal operations is fully characterized by the second law of thermodynamics. Specifically, we prove that whether a quantum state with quantum coherence is convertible to another by a thermal operation with a correlated catalyst is completely determined by the free energy ordering. Unlike previous attempts, our setting does not resort to any additional external coherent assist, providing a faithful operational characterization of thermodynamic state transformation.
In recent years we have witnessed a concentrated effort to make sense of thermodynamics for small-scale systems. One of the main difficulties is to capture a suitable notion of work that models realistically the purpose of quantum machines, in an analogous way to the role played, for macroscopic machines, by the energy stored in the idealisation of a lifted weight. Despite several attempts to resolve this issue by putting forward specific models, these are far from realistically capturing the transitions that a quantum machine is expected to perform. In this work, we adopt a novel strategy by considering arbitrary kinds of systems that one can attach to a quantum thermal machine and defining work quantifiers . These are functions that measure the value of a transition and generalise the concept of work beyond those models familiar from phenomenological thermodynamics. We do so by imposing simple operational axioms that any reasonable work quantifier must fulfil and by deriving from them stringent mathematical condition with a clear physical interpretation. Our approach allows us to derive much of the structure of the theory of thermodynamics without taking the definition of work as a primitive. We can derive, for any work quantifier , a quantitative second law in the sense of bounding the work that can be performed using some non-equilibrium resource by the work that is needed to create it. We also discuss in detail the role of reversibility and correlations in connection with the second law. Furthermore, we recover the usual identification of work with energy in degrees of freedom with vanishing entropy as a particular case of our formalism. Our mathematical results can be formulated abstractly and are general enough to carry over to other resource theories than quantum thermodynamics.
Abstract The thermodynamic properties of quantum heat engines are stochastic owing to the presence of thermal and quantum fluctuations. We here experimentally investigate the efficiency and nonequilibrium entropy production statistics of a spin-1/2 quantum Otto cycle in a nuclear magnetic resonance setup. We first study the correlations between work and heat within a cycle by extracting their joint distribution for different driving times. We show that near perfect correlation, corresponding to the tight-coupling condition between work and heat, can be achieved. In this limit, the reconstructed efficiency distribution is peaked at the deterministic thermodynamic efficiency, and fluctuations are strongly suppressed. We further successfully test the second law in the form of a joint fluctuation relation for work and heat in the quantum cycle. Our results characterize the statistical features of a small-scale thermal machine in the quantum domain, and provide means to control them.