Noncommutativity of observables is a defining feature of quantum physics. It plays a fundamental role in the formulation of the uncertainty principle for complementary variables and strongly affects the thermodynamic behavior of systems with noncommuting, that is, non-Abelian, conserved quantities. We here derive extensions of the first and second laws of thermodynamics, including nonequilibrium fluctuation relations, for driven quantum systems. We identify an additional non-Abelian contribution to the energy and entropy balances, without which these relations would be violated. This contribution can be harnessed to enhance both work extraction and nonequilibrium currents compared to what is achieved in commuting thermodynamics. These results demonstrate that noncommutativity is a potentially valuable thermodynamic resource.
Noncommutativity of observables is a defining feature of quantum physics. It plays a fundamental role in the formulation of the uncertainty principle for complementary variables and strongly affects the thermodynamic behavior of systems with noncommuting, that is, non-Abelian, conserved quantities. We here derive extensions of the first and second laws of thermodynamics, including nonequilibrium fluctuation relations, for driven quantum systems. We identify an additional non-Abelian contribution to the energy and entropy balances, without which these relations would be violated. This contribution can be harnessed to enhance both work extraction and nonequilibrium currents compared to what is achieved in commuting thermodynamics. These results demonstrate that noncommutativity is a potentially valuable thermodynamic resource.
We derive detailed and intergral fluctuation relations as well as a thermodynamic uncertainty relation constraining the exchange statistics of an arbitrary number of noncommuting conserved quantities among two quantum systems in transport setups arbitrary far from equilibrium. These universal relations, valid without the need of any efficacy parameter, extend the well-known heat exchange fluctuation theorems for energy and particle transport to the case of non-Abelian quantum transport, where the noncommutativity of the charges allows going beyond standard thermodynamic behavior. In particular, we show that this can lead to enhanced precision in the current fluctuations, and it allows for the inversion of all currents against their affinity biases.
A central open question in quantum thermodynamics is the identification of thermodynamic entropy away from equilibrium. Although thermodynamic entropy coincides with the von Neumann entropy for a Gibbs state at equilibrium, the thermodynamic role of quantum coherence generated during nonequilibrium evolution remains unclear. Here, we show that von Neumann entropy does not, in general, represent the thermodynamic entropy governing heat exchange in coherent nonequilibrium quantum systems. By integrating the resource theory of quantum coherence with thermodynamic principles, we develop a general framework for nonequilibrium quantum thermodynamics. We identify thermodynamic entropy with the energy entropy derived from energy-measurement statistics and introduce a dynamical temperature extending the equilibrium concept to nonequilibrium states. Consequently, we obtain an exact entropy-balance relation separating the entropy flux associated with heat exchange from the coherence-loss contribution to entropy production, establishing an operational connection between quantum coherence, heat flow, and total entropy change. Unlike approaches relying on equilibrium reference states or stationary Gibbs ensembles, our framework uses instantaneous dynamical quantities and remains valid throughout transient nonequilibrium evolution. It provides consistent dynamical definitions of temperature, work, heat, and free energy. Applying the formalism to an exactly solvable open quantum system, we show that the first and second laws hold throughout transient evolution and that equilibrium thermodynamics emerges dynamically in the weak-coupling long-time limit. Our results establish a unified framework for coherent nonequilibrium quantum thermodynamics and suggest opportunities for controlling heat dissipation through coherence engineering in quantum thermal technologies.
We extend entropy production to a deeply quantum regime involving noncommuting conserved quantities. Consider a unitary transporting conserved quantities (“charges”) between two systems initialized in thermal states. Three common formulas model the entropy produced. They respectively cast entropy as an extensive thermodynamic variable, as an information-theoretic uncertainty measure, and as a quantifier of irreversibility. Often, the charges are assumed to commute with each other (e.g., energy and particle number). Yet quantum charges can fail to commute. Noncommutation invites generalizations, which we posit and justify, of the three formulas. The noncommutation of charges, we find, breaks the equivalence of the formulas. Furthermore, different formulas quantify different physical effects of the noncommutation of charges on entropy production. For instance, entropy production can signal contextuality—true nonclassicality—by becoming nonreal. This work opens up stochastic thermodynamics to noncommuting—and so particularly quantum—charges. Published by the American Physical Society 2024
Thermodynamic uncertainty principles make up one of the few rare anchors in the largely uncharted waters of nonequilibrium systems, the fluctuation theorems being the more familiar. In this work we aim to trace the uncertainties of thermodynamic quantities in nonequilibrium systems to their quantum origins, namely, to the quantum uncertainty principles. Our results enable us to make this categorical statement: For Gaussian systems, thermodynamic functions are functionals of the Robertson-Schrödinger uncertainty function, which is always non-negative for quantum systems, but not necessarily so for classical systems. Here, quantum refers to noncommutativity of the canonical operator pairs. From the nonequilibrium free energy, we succeeded in deriving several inequalities between certain thermodynamic quantities. They assume the same forms as those in conventional thermodynamics, but these are nonequilibrium in nature and they hold for all times and at strong coupling. In addition we show that a fluctuation-dissipation inequality exists at all times in the nonequilibrium dynamics of the system. For nonequilibrium systems which relax to an equilibrium state at late times, this fluctuation-dissipation inequality leads to the Robertson-Schrödinger uncertainty principle with the help of the Cauchy-Schwarz inequality. This work provides the microscopic quantum basis to certain important thermodynamic properties of macroscopic nonequilibrium systems.
A consistent theory of non-equilibrium thermodynamics for Markovian open quantum systems has been developed in the late seventies in analogy with Classical Irreversible Thermodynamics. The time-evolution of these open systems is usually described by means of effective master equations in Lindblad form, that turn out to be reliable when there is a separation of time-scales between system and environment, such that memory effects are negligible and the so-called Markovian approximation is justified. In this framework, the variations of energy and entropy in the system are consistently described, distinguishing between heat and work contributions and providing a statement of the second law of thermodynamics as positivity of the entropy production.\nHowever, there is empirical evidence that many physical systems like photosynthetic complexes,\nopto-mechanical resonators and superconducting qubits, just to mention a few, experience more general non-Markovian dynamics. The formulation of the laws of thermodynamics in a non-Markovian setting is matter of current research and represents the main topic of the present work. As a first step, we show that the entropy production defined as in the Markovian case can be negative for a class of non-Markovian dynamics. We argue that this outcome should not be interpreted as a violation of the second law of thermodynamics because the environment must be explicitly taken into account in the balance of entropy in the non-Markovian setting. In order to justify this claim we adopt a more general point of view, studying a closed bipartite quantum system, such that each of the two subsystems plays the role of a finite environment out of equilibrium for the other one. We concentrate on the balance of energy first and construct an effective Hamiltonian for each subsystem using physically reasonable requirements; then we define heat and work as in the standard Markovian treatment, with the effective Hamiltonian replacing the free Hamiltonian. It turns out that, in our framework, the work power is perfectly balanced between subsystems, while the correlations can store a part of energy locally inaccessible and exchange it with both subsystems in the form of heat.\nConcerning the balance of entropy, a quite general formulation of the second law of thermodynamics can be given as follows: under the assumption of a factorized initial state for the compound system, the sum of the total variations of the entropies in the two subsystems is always nonnegative. We show with an explicit example that this general formulation does not correspond to the statement presented in the framework of Markovian master equations, which should not be considered a priori the second law of thermodynamics.\nIn the last part of the thesis we concentrate of the so-called fluctuation relations, that are results extending the thermodynamic formalism beyond the behavior of average quantities. After reviewing the main theoretical outcomes, such as the Jarzynski equality and the Crooks fluctuation theorem, we describe a proposal to access experimentally the work performed on an ensemble of diatomic molecules by a time-dependent electric field coupled with their vibrational degree of freedom. This procedure could then be used to test the quantum Jarzynski equality. With respect to the results so far appeared in the literature, in which the left-hand side of the equality is inferred from an experiment and the right-hand side is computed according to a model, in our proposed setting we should be able to estimate from the experiment both the left-hand side and the right-hand side of the equality, independently.
The first part of this thesis focuses on verifying the quantum nonequilibrium work relation in the presence of decoherence. The nonequilibrium work relation is a generalization of the second law of thermodynamics that links nonequilibrium work measurements to equilibrium free energies via an equality. Despite being well established for classical systems, a quantum work relation is conceptually difficult to construct for systems that interact with their environment. We argue that for a quantum system which undergoes decoherence but not dissipation, these conceptual difficulties do not arise and the work relation can be proven similarly to the case of an isolated system. This result is accompanied by an experimental demonstration using trapped ions. The second part of this thesis examines the relationship between quantum work and coherence by constructing analogous quantities in classical physics. It has recently been shown that quantum coherence can function as a resource for work extraction. Furthermore, it has been suggested that this property could be a truly quantum aspect of thermodynamics with no classical analog. We examine this assertion within the framework of classical Hamiltonian mechanics and canonical quantization. For classical states we define a so called non-uniformity measure and show that it is a resource for work extraction similar to quantum coherence. Additionally, we show that work extracted from non-uniformity and coherence agree in the classical limit. This calls into question the idea that coherence qualitatively separates classical and quantum thermodynamics. The final part of this thesis explores the connection between decoherence and adiabatic (quasistatic) driving. This topic is inspired by an experiment where it was seen that strong dephasing suppressed energy level transitions. Using a perturbative method we investigate this mechanism in the regime of small to moderate decoherence rate and ask if decoherence can help suppress energy transitions when compared with an adiabatic process without decoherence. We find that strategies that include decoherence are inferior to those where decoherence is absent.