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arXiv:1601.05799 · Physical Review X

Fluctuating Work: From Quantum Thermodynamical Identities to a Second Law Equality

Alvaro Martin Alhambra, Lluís Masanes, Jonathan Oppenheim, Christopher Perry

Published Oct 24, 2016• 99 citations
arXivHTMLPDF

Abstract

The second law of thermodynamics plays an important role in both everyday life---think of hot coffee cooling off---and a range of scientific disciplines. Now, researchers prove a more accurate version of the second law, which states precisely by how much the hot coffee cools off, as well as being relevant to small quantum systems.
DOI
10.1103/physrevx.6.041017

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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.
Classical thermodynamics is unrivalled in its range of applications and relevance to everyday life. It enables a description of complex systems, made up of microscopic particles, in terms of a small number of macroscopic quantities, such as work and entropy. As systems get ever smaller, fluctuations of these quantities become increasingly relevant, prompting the development of stochastic thermodynamics. Recently we have seen a surge of interest in exploring the quantum regime, where the origin of fluctuations is quantum rather than thermal. Many questions, such as the role of entanglement and the emergence of thermalisation, lie wide open. Answering these questions may lead to the development of quantum heat engines and refrigerators, as well as to vitally needed simple descriptions of quantum many-body systems.
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.
Since the days of Boltzmann the foundation of thermodynamics has been subject to an ongoing discussion. Various problems like the precise definition of entropy, the origin of the second law, etc. have always been issues. For a long time the discussion has not been in the center of interest, for statistical physics work extremely well from a practical point of view. But now, as research deals with single small objects like molecules or atoms, the question arises whether or not thermodynamics are applicable to them, which leads back to the old question of the foundation of thermodynamics. We examine whether thermodynamics can be viewed as emerging from Schrödinger-type quantum dynamics. Therefore we partially transfer concepts of thermodynamical behavior in Gamma-space to the Hilbertspace of compound systems. Central roles play the local Von Neumann entropy of a system and the inevitability of entanglement with its environment, causing it to increase.
A version of the second law of thermodynamics states that one cannot lower the energy of an isolated system by a cyclic operation. We prove this law without introducing statistical ensembles and by resorting only to quantum mechanics. We choose the initial state as a pure quantum state whose energy is almost E_0 but not too sharply concentrated at energy eigenvalues. Then after an arbitrary unitary time evolution which follows a typical "waiting time", the probability of observing the energy lower than E_0 is proved to be negligibly small.