In this paper, our focus is on the question whether the cyclic process of coupling and decoupling of a charged quantum magneto-oscillator or a charged quantum electro-oscillator from a quantum heat bath can lead to a violation of the second law of thermodynamics. The results obtained from the thermodynamic entropic point of view are compared with that obtained from the von Neumann entropic perspective. As far as the validity of thermodynamic laws is concerned, the thermodynamic entropy can be chosen judiciously, so that no problem arises in its interpretation.
In this paper, our focus is on the question whether the cyclic process of coupling and decoupling of a charged quantum magneto-oscillator or a charged quantum electro-oscillator from a quantum heat bath can lead to a violation of the second law of thermodynamics. The results obtained from the thermodynamic entropic point of view are compared with that obtained from the von Neumann entropic perspective. As far as the validity of thermodynamic laws is concerned, the thermodynamic entropy can be chosen judiciously, so that no problem arises in its interpretation.
Quantum entanglement can cause the efficiency of a heat engine to be greater than the efficiency of the Carnot cycle. However, this does not mean a violation of the second law of thermodynamics, since there is no local equilibrium for pure quantum states, and, in the absence of local equilibrium, thermodynamics cannot be formulated correctly. Von Neumann entropy is not a thermodynamic quantity, although it can characterize the ordering of a system. In the case of the entanglement of the particles of the system with the environment, the concept of an isolated system should be refined. In any case, quantum correlations cannot lead to a violation of the second law of thermodynamics in any of its formulations. This article is devoted to a technical discussion of the expected results on the role of quantum entanglement in thermodynamics.
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.
Recent theoretical and experimental work on the foundations of statistical mechanics and thermodynamics has shown that quantum pure states typically evolve to thermal equilibrium. We focus on formulating the second law of thermodynamics for these states. The standard quantum von Neumann quantum entropy is constant during equilibration, S^{vN}=0, in apparent conflict with the entropy increase of the second law, ΔS_{univ} > 0. We explore a recently developed entropy S_{univ}^Q for a pure state and test its behavior in simulations of a model system and environment evolving in time with heat flow to equilibrium. We find that the entropy approaches the correct classical value in a type of classical limit with weak coupling. With stronger coupling, we find a new source of quantum "excess entropy production," which has its origin in the quantum spreading of the wavepacket. Are there quantum thermodynamic effects related to this new source of entropy? To test this, we developed a model for a small variable temperature quantum oscillator bath. We performed simulations where two small baths are linked by a system, with unequal couplings to the baths. The model evolves to a novel type of equilibrium state with unequal temperatures in the baths, with heat flow from cold to hot along the path to equilibrium. We give an account of this behavior in terms of the second law with the quantum entropy S_{univ}^Q. The new formulation of the second law thus appears well-founded and fruitful, with surprising new quantum thermodynamic effects that may still be awaiting discovery, for example in molecules or systems far from equilibrium. \n\nThis dissertation includes previously published and unpublished co-authored material.
The Brownian motion of a quantum particle in a harmonic confining potential and coupled to harmonic quantum thermal bath is exactly solvable. Though this system presents at high temperatures a pedagogic example to explain the laws of thermodynamics, it is shown that at low enough temperatures the stationary state is non-Gibbsian due to an entanglement with the bath. In physical terms, this happens when the cloud of bath modes around the particle starts to play a nontrivial role, namely, when the bath temperature T is smaller than the coupling energy. Indeed, equilibrium thermodynamics of the total system, particle plus bath, does not imply standard equilibrium thermodynamics for the particle itself at low T. Various formulations of the second law are found to be invalid at low T. First, the Clausius inequality can be violated, because heat can be extracted from the zero point energy of the cloud of bath modes. Second, when the width of the confining potential is suddenly changed, there occurs a relaxation to equilibrium during which the entropy production is partly negative. In this process the energy put on the particle does not relax monotonically, but oscillates between particle and bath, even in the limit of strong damping. Third, for nonadiabatic changes of system parameters the rate of energy dissipation can be negative, and, out of equilibrium, cyclic processes are possible which extract work from the bath. Conditions are put forward under which perpetuum mobility of the second kind, having one or several work extraction cycles, enter the realm of condensed matter physics. Fourth, it follows that the equivalence between different formulations of the second law (e.g., those by Clausius and Thomson) can be violated at low temperatures. These effects are the consequence of quantum entanglement in the presence of the slightly off-equilibrium nature of the thermal bath, and become important when the characteristic quantum time scale variant Planck's over 2pi /k(B)T is larger than or comparable to other time scales of the system. They show that there is no general consensus between standard thermodynamics and quantum mechanics. The known agreements occur only due to the weak coupling limit, which does not pertain to low temperatures. Experimental setups for testing the effects are discussed.
The quantum thermodynamic behaviour of a charged oscillator in the presence of a magnetic field and coupled to a heat bath through different coupling schemes is obtained analytically. It is shown that finite dissipation substitutes the zero-coupling result of exponential decay of entropy by a power law behaviour at low temperature. For the coordinate-coordinates coupling scheme the low temperature explicit results for the case of Ohmic, exponentially correlated and more generalized heat bath models are derived. In all the above mentioned cases free energy and entropy vanish linearly with temperature (T) as T→0 in conformity with Nernst's theorem. It is seen that coordinate (velocity)-velocities (coordinates) coupling is much more beneficial than the coordinate-coordinates coupling to ensure third law of thermodynamics. The case of radiation heat bath shows T3 decay behaviour for entropy as T→0. It is observed that at low temperature free energy and entropy decay faster for the velocity-velocities scheme than any other coupling schemes. This implies velocity-velocities coupling scheme is the most advantageous coupling scheme in restoring the third law of thermodynamics. It is shown that the low temperature thermodynamic functions are independent of magnetic field for all the above mentioned cases except the without dissipation case.
Recently Allahverdyan and Nieuwenhuizen (cond-mat/0006404) argued that the second law of thermodynamics may be violated in a quantum system as a "consequence of quantum coherence in the presence of the slightly off-equilibrium nature of the bath." By using a standard result about relative entropy, we prove rigorously that the second law is never violated (and, in particular, a perpetual motion of the second kind can never be realized) in quantum systems no matter how strong ``quantum coherence'' is or no matter how far one goes from equilibrium.