The Second Law of Thermodynamics is considered to be one of the most fundamental and important laws of Physics. Both Clausius and Kelvin reformulated the Second Law as statements concerning the behaviour of two communicating systems, set to interact at different temperatures. The average positive entropy production of any process, described by the Second Law, is often understood as a "thermodynamic arrow of time" capable of discerning the direction in which physical events should arrange. By studying a microscopic system described by two initially correlated qubits, in this thesis we explore the phenomenon of reverse energy flow. Differently from an often standard uncorrelated case, the correlated one shows properties that seem to suggest that a further generalization of both Clausius and Kelvin's statements is needed
The Second Law of Thermodynamics is considered to be one of the most fundamental and important laws of Physics. Both Clausius and Kelvin reformulated the Second Law as statements concerning the behaviour of two communicating systems, set to interact at different temperatures. The average positive entropy production of any process, described by the Second Law, is often understood as a "thermodynamic arrow of time" capable of discerning the direction in which physical events should arrange. By studying a microscopic system described by two initially correlated qubits, in this thesis we explore the phenomenon of reverse energy flow. Differently from an often standard uncorrelated case, the correlated one shows properties that seem to suggest that a further generalization of both Clausius and Kelvin's statements is needed
Recent research on the thermodynamic arrow of time, at the microscopic scale, has questioned the universality of its direction. Theoretical studies showed that quantum correlations can be used to revert the natural heat flow (from the hot body to the cold one), posing an apparent challenge to the second law of thermodynamics. Such an "anomalous" heat current was observed in a recent experiment (K. Micadei et al., arXiv:1711.03323), by employing two spin systems initially quantum correlated. Nevertheless, the precise relationship between this intriguing phenomenon and the initial conditions that allow it is not fully evident. Here, we address energy transfer in a wider perspective, identifying a nonclassical contribution that applies to the reversion of the heat flow as well as to more general forms of energy exchange. We derive three theorems that describe the energy transfer between two microscopic systems, for arbitrary initial bipartite states. Using these theorems, we obtain an analytical bound showing that certain type of quantum coherence can optimize such a process, outperforming incoherent states. This genuine quantum advantage is corroborated through a characterization of the energy transfer between two qubits. For this system, it is shown that a large enough amount of coherence is necessary and sufficient to revert the thermodynamic arrow of time. As a second crucial consequence of the presented theorems, we introduce a class of nonequilibrium states that only allow unidirectional energy flow. In this way, we broaden the set where the standard Clausius statement of the second law applies.
The second law permits the prediction of the direction of natural processes, thus defining a thermodynamic arrow of time. However, standard thermodynamics presupposes the absence of initial correlations between interacting systems. We here experimentally demonstrate the reversal of the arrow of time for two initially quantum correlated spins-1/2, prepared in local thermal states at different temperatures, employing a Nuclear Magnetic Resonance setup. We observe a spontaneous heat flow from the cold to the hot system. This process is enabled by a trade off between correlations and entropy that we quantify with information-theoretical quantities.
This work investigates the fundamental connection between quantum mechanics and thermodynamics through the concept of the arrow of time. While the second law of thermodynamics identifies the arrow of time with the monotonic increase of entropy in isolated systems, closed quantum systems evolve unitarily and conserve von Neumann entropy, making the origin of irreversibility less apparent. Here we establish a no-go theorem proving that correlations in unknown states of closed quantum systems cannot be universally removed by any physical operation. This result demonstrates that correlation generation is inherently irreversible, providing a microscopic and universal basis for the arrow of time. In thermodynamic settings, this irreversibility ensures that heat flows spontaneously from hotter to colder subsystems, reproducing the Clausius formulation of the second law. More generally, the irreversible growth of correlations explains entropy increase, the approach to equilibrium, and decoherence as observable manifestations of the same principle. Our findings ground a quantum-mechanical foundation for the second law of thermodynamics and demonstrate the universality of the arrow of time.
The second law of classical equilibrium thermodynamics, based on the positivity of entropy production, asserts that any process occurs only in a direction that some information may be lost (flow out of the system) due to the irreversibility inside the system. However, any thermodynamic system can exhibit fluctuations in which negative entropy production may be observed. In particular, in stochastic quantum processes due to quantum correlations and also memory effects we may see the reversal energy flow (heat flow from the cold system to the hot system) and the backflow of information into the system that leads to the negativity of the entropy production which is an apparent violation of the Second Law. In order to resolve this apparent violation, we will try to properly extend the Second Law to quantum processes by incorporating information explicitly into the Second Law. We will also provide a thermodynamic operational meaning for the flow and backflow of information. Finally, it is shown that negative and positive entropy production can be described by a quantum thermodynamic force.
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.
Abstract Microscopic physical laws are time-symmetric, hence, a priori there exists no preferential temporal direction. However, the second law of thermodynamics allows one to associate the “forward” temporal direction to a positive variation of the total entropy produced in a thermodynamic process, and a negative variation with its “time-reversal” counterpart. This definition of a temporal axis is normally considered to apply in both classical and quantum contexts. Yet, quantum physics admits also superpositions between forward and time-reversal processes, whereby the thermodynamic arrow of time becomes quantum-mechanically undefined. In this work, we demonstrate that a definite thermodynamic time’s arrow can be restored by a quantum measurement of entropy production, which effectively projects such superpositions onto the forward (time-reversal) time-direction when large positive (negative) values are measured. Finally, for small values (of the order of plus or minus one), the amplitudes of forward and time-reversal processes can interfere, giving rise to entropy-production distributions featuring a more or less reversible process than either of the two components individually, or any classical mixture thereof.