Fluctuations of thermodynamic observables, such as heat and work, contain relevant information on the underlying physical process. These fluctuations are however not taken into account in the traditional laws of thermodynamics. While the second law is extended to fluctuating systems by the celebrated fluctuation theorems, the first law is generally believed to hold even in the presence of fluctuations. Here we show that in the presence of quantum fluctuations, also the first law of thermodynamics may break down. This happens because quantum mechanics imposes constraints on the knowledge of heat and work. To illustrate our results, we provide a detailed case-study of work and heat fluctuations in a quantum heat engine based on a circuit QED architecture. We find probabilistic violations of the first law and show that they are closely connected to quantum signatures related to negative quasi-probabilities. Our results imply that in the presence of quantum fluctuations, the first law of thermodynamics may not be applicable to individual experimental runs.
Fluctuations of thermodynamic observables, such as heat and work, contain relevant information on the underlying physical process. These fluctuations are however not taken into account in the traditional laws of thermodynamics. While the second law is extended to fluctuating systems by the celebrated fluctuation theorems, the first law is generally believed to hold even in the presence of fluctuations. Here we show that in the presence of quantum fluctuations, also the first law of thermodynamics may break down. This happens because quantum mechanics imposes constraints on the knowledge of heat and work. To illustrate our results, we provide a detailed case-study of work and heat fluctuations in a quantum heat engine based on a circuit QED architecture. We find probabilistic violations of the first law and show that they are closely connected to quantum signatures related to negative quasi-probabilities. Our results imply that in the presence of quantum fluctuations, the first law of thermodynamics may not be applicable to individual experimental runs.
A heat engine undergoes a cyclic operation while in equilibrium with the net result of conversion of heat into work. Quantum effects such as superposition of states can improve an engine's efficiency by breaking detailed balance, but this improvement comes at a cost due to excess entropy generated from collapse of superpositions on measurement. We quantify these competing facets for a quantum ratchet composed of an ensemble of pairs of interacting two-level atoms. We suggest that the measurement postulate of quantum mechanics is intricately connected to the second law of thermodynamics. More precisely, if quantum collapse is not inherently random, then the second law of thermodynamics can be violated. Our results challenge the conventional approach of simply quantifying quantum correlations as a thermodynamic work deficit.
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.
At the very foundation of the second law of thermodynamics lies the fact that no heat engine operating between two reservoirs of temperatures T C ⩽ T H can outperform the ideal Carnot engine: 〈 W 〉/〈 Q H 〉 ⩽ 1 − T C / T H . This inequality follows from an exact fluctuation relation involving the nonequilibrium work W and heat exchanged with the hot bath Q H . In a previous work (Sinitsyn 2011 J. Phys. A: Math. Theor. 44 405001) this fluctuation relation was obtained under the assumption that the heat engine undergoes a stochastic jump process. Here we provide the general quantum derivation, and also extend it to the case of refrigerators, in which case Carnot's statement reads 〈 Q C 〉/|〈 W 〉| ⩽ ( T H / T C − 1) −1 .
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.
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.
The standard approach to deriving fluctuation theorems fails to capture the effect of quantum correlation and coherence in the initial state of the system.Here, we overcome this difficulty and derive the heat-exchange-fluctuation theorem in the full quantum regime by showing that the energy exchange between two locally thermal states in the presence of initial quantum correlations is faithfully captured by a quasiprobability distribution.Its negativities, being associated with proofs of contextuality, are proxies of nonclassicality.We discuss the thermodynamic interpretation of negative probabilities and provide heat-flow inequalities that can only be violated in their presence.Remarkably, testing these fully quantum inequalities, at an arbitrary dimension, is no more difficult than testing traditional fluctuation theorems.We test these results on data collected in a recent experiment studying the heat transfer between two qubits and give examples for the capability of witnessing negative probabilities at higher dimensions.