Thermodynamics is traditionally constrained to the study of macroscopic systems whose energy fluctuations are negligible compared to their average energy. Here, we push beyond this thermodynamic limit by developing a mathematical framework to rigorously address the problem of thermodynamic transformations of finite-size systems. More formally, we analyse state interconversion under thermal operations and between arbitrary energy-incoherent states. We find precise relations between the optimal rate at which interconversion can take place and the desired infidelity of the final state when the system size is sufficiently large. These so-called second-order asymptotics provide a bridge between the extreme cases of single-shot thermodynamics and the asymptotic limit of infinitely large systems. We illustrate the utility of our results with several examples. We first show how thermodynamic cycles are affected by irreversibility due to finite-size effects. We then provide a precise expression for the gap between the distillable work and work of formation that opens away from the thermodynamic limit. Finally, we explain how the performance of a heat engine gets affected when one of the heat baths it operates between is finite. We find that while perfect work cannot generally be extracted at Carnot efficiency, there are conditions under which these finite-size effects vanish. In deriving our results we also clarify relations between different notions of approximate majorisation.
Thermodynamics is traditionally constrained to the study of macroscopic systems whose energy fluctuations are negligible compared to their average energy. Here, we push beyond this thermodynamic limit by developing a mathematical framework to rigorously address the problem of thermodynamic transformations of finite-size systems. More formally, we analyse state interconversion under thermal operations and between arbitrary energy-incoherent states. We find precise relations between the optimal rate at which interconversion can take place and the desired infidelity of the final state when the system size is sufficiently large. These so-called second-order asymptotics provide a bridge between the extreme cases of single-shot thermodynamics and the asymptotic limit of infinitely large systems. We illustrate the utility of our results with several examples. We first show how thermodynamic cycles are affected by irreversibility due to finite-size effects. We then provide a precise expression for the gap between the distillable work and work of formation that opens away from the thermodynamic limit. Finally, we explain how the performance of a heat engine gets affected when one of the heat baths it operates between is finite. We find that while perfect work cannot generally be extracted at Carnot efficiency, there are conditions under which these finite-size effects vanish. In deriving our results we also clarify relations between different notions of approximate majorisation.
We address the problem of exact and approximate transformation of quantum dichotomies in the asymptotic regime, i.e., the existence of a quantum channel E mapping ρ1⊗n into ρ2⊗Rnn with an error ϵn (measured by trace distance) and σ1⊗n into σ2⊗Rnn exactly, for a large number n . We derive second-order asymptotic expressions for the optimal transformation rate Rn in the small-, moderate-, and large-deviation error regimes, as well as the zero-error regime, for an arbitrary pair (ρ1,σ1) of initial states and a commuting pair (ρ2,σ2) of final states. We also prove that for σ1 and σ2 given by thermal Gibbs states, the derived optimal transformation rates in the first three regimes can be attained by thermal operations. This allows us, for the first time, to study the second-order asymptotics of thermodynamic state interconversion with fully general initial states that may have coherence between different energy eigenspaces. Thus, we discuss the optimal performance of thermodynamic protocols with coherent inputs and describe three novel resonance phenomena allowing one to significantly reduce transformation errors induced by finite-size effects. What is more, our result on quantum dichotomies can also be used to obtain, up to second-order asymptotic terms, optimal conversion rates between pure bipartite entangled states under local operations and classical communication. Published by the American Physical Society 2024
The second law of thermodynamics places constraints on state transformations. It applies to systems composed of many particles, however, we are seeing that one can formulate laws of thermodynamics when only a small number of particles are interacting with a heat bath. Is there a second law of thermodynamics in this regime? Here, we find that for processes which are approximately cyclic, the second law for microscopic systems takes on a different form compared to the macroscopic scale, imposing not just one constraint on state transformations, but an entire family of constraints. We find a family of free energies which generalize the traditional one, and show that they can never increase. The ordinary second law relates to one of these, with the remainder imposing additional constraints on thermodynamic transitions. We find three regimes which determine which family of second laws govern state transitions, depending on how cyclic the process is. In one regime one can cause an apparent violation of the usual second law, through a process of embezzling work from a large system which remains arbitrarily close to its original state. These second laws are relevant for small systems, and also apply to individual macroscopic systems interacting via long-range interactions. By making precise the definition of thermal operations, the laws of thermodynamics are unified in this framework, with the first law defining the class of operations, the zeroth law emerging as an equivalence relation between thermal states, and the remaining laws being monotonicity of our generalized free energies.
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 optimal efficiency of quantum (or classical) heat engines whose heat baths are n-particle systems is given by the strong large deviation. We give the optimal work extraction process as a concrete energy-preserving unitary time evolution among the heat baths and the work storage. We show that our optimal work extraction turns the disordered energy of the heat baths to the ordered energy of the work storage, by evaluating the ratio of the entropy difference to the energy difference in the heat baths and the work storage, respectively. By comparing the statistical mechanical optimal efficiency with the macroscopic thermodynamic bound, we evaluate the accuracy of the macroscopic thermodynamics with finite-size heat baths from the statistical mechanical viewpoint. We also evaluate the quantum coherence effect on the optimal efficiency of the cycle processes without restricting their cycle time by comparing the classical and quantum optimal efficiencies.
Quantum systems strongly coupled to many-body systems equilibrate to the reduced state of a global thermal state, deviating from the local thermal state of the system as it occurs in the weak-coupling limit. Taking this insight as a starting point, we study the thermodynamics of systems strongly coupled to thermal baths. First, we provide strong-coupling corrections to the second law applicable to general systems in three of its different readings: As a statement of maximal extractable work, on heat dissipation, and bound to the Carnot efficiency. These corrections become relevant for small quantum systems and vanish in first order in the interaction strength. We then move to the question of power of heat engines, obtaining a bound on the power enhancement due to strong coupling. Our results are exemplified on the paradigmatic non-Markovian quantum Brownian motion.
Sadi Carnot's theorem regarding the maximum efficiency of heat engines is considered to be of fundamental importance in thermodynamics. This theorem famously states that the maximum efficiency depends only on the temperature of the heat baths used by the engine, but not on the specific structure of baths. Here, we show that when the heat baths are finite in size, and when the engine operates in the quantum nanoregime, a revision to this statement is required. We show that one may still achieve the Carnot efficiency, when certain conditions on the bath structure are satisfied; however if that is not the case, then the maximum achievable efficiency can reduce to a value which is strictly less than Carnot. We derive the maximum efficiency for the case when one of the baths is composed of qubits. Furthermore, we show that the maximum efficiency is determined by either the standard second law of thermodynamics, analogously to the macroscopic case, or by the non increase of the max relative entropy, which is a quantity previously associated with the single shot regime in many quantum protocols. This relative entropic quantity emerges as a consequence of additional constraints, called generalized free energies, that govern thermodynamical transitions in the nanoregime. Our findings imply that in order to maximize efficiency, further considerations in choosing bath Hamiltonians should be made, when explicitly constructing quantum heat engines in the future. This understanding of thermodynamics has implications for nanoscale engineering aiming to construct small thermal machines.