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.

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A suitable way of quantifying work for microscopic quantum systems has been constantly debated in the field of quantum thermodynamics. One natural approach is to measure the average increase in energy of an ancillary system, called the battery, after a work extraction protocol. The quality of energy extracted is usually argued to be good by quantifying higher moments of the energy distribution, or by restricting the amount of entropy to be low. This limits the amount of heat contribution to the energy extracted, but does not completely prevent it. We show that the definition of 'work' is crucial. If one allows for a definition of work that tolerates a non-negligible entropy increase in the battery, then a small scale heat engine can possibly exceed the Carnot efficiency. This can be done without using any additional resources such as coherence or correlations, and furthermore can be achieved even when one of the heat baths is finite in size.@en

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. @en

In the study of thermodynamics for nanoscale quantum systems, a family of quantities known as generalized free energies have been derived as necessary and sufficient conditions that govern state transitions. These free energies become important especially in the regime where the system of interest consists of only a few (quantum) particles. In this work, we introduce a family of smoothed generalized free energies, by constructing explicit smoothing procedures that maximize or minimize the free energy over an ball of quantum states. In contrast to previously known smoothed free energies, these quantities now allow us to make an operational statement for approximate thermodynamic state transitions. We show that these smoothed quantities converge to the standard free energy in the thermodynamic limit.

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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.

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Quantum thermodynamics is a research field that aims at fleshing out the ultimate limits of thermodynamic processes in the deep quantum regime. A complete picture of thermodynamical processes naturally allows for auxiliary systems dubbed 'catalysts', i.e., any physical systems facilitating state transformations while remaining essentially intact in their state, like an auxiliary system, a clock, or an actual catalyst. In this work, we present a comprehensive analysis of the power and limitation of such thermal catalysis. Specifically, we provide a family of optimal catalysts that can be returned with minimal trace distance error after facilitating a state transformation process. To incorporate the genuine physical role of a catalyst, we identify very significant restrictions on arbitrary state transformations under dimension or mean energy bounds, using methods of convex relaxations. We discuss the implication of these findings on possible thermodynamic state transformations in the quantum regime.

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