The Second Law of Thermodynamics at the Microscopic Scale

Fernando G. S. L. Brandão, Michał Horodecki, Nelly H. Y. Ng +2 more

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.

Raymond A Nelson

Abstract : Work is conducted which shows that irreversible macroscopic behavior can result from reversible microscopic mechanics or, more specifically, how the second law of thermodynamics can be a consequence of the Schrodinger equation. (Author)

Alberto Frigerio, Vittorio Gorini, Maurizio Verri

Vladislav Čápek, O. M. Frege

Paolo Glorioso, Hong Liu

The second law of thermodynamics states that for a thermally isolated system entropy never decreases. Most physical processes we observe in nature involve variations of macroscopic quantities over spatial and temporal scales much larger than microscopic molecular collision scales and thus can be considered as in local equilibrium. For a many-body system in local equilibrium a stronger version of the second law applies which says that the entropy production at each spacetime point should be non-negative. In this paper we provide a proof of the second law for such systems and a first derivation of the local second law. For this purpose we develop a general non-equilibrium effective field theory of slow degrees of freedom from integrating out fast degrees of freedom in a quantum many-body system and consider its classical limit. The key elements of the proof are the presence of a $Z_2$ symmetry, which can be considered as a proxy for local equilibrium and micro-time-reversibility, and a classical remnant of quantum unitarity. The $Z_2$ symmetry leads to a local current from a procedure analogous to that used in the Noether theorem. Unitarity leads to a definite sign of the divergence of the current. We also discuss the origin of an arrow of time, as well as the coincidence of causal and thermodynamical arrows of time. Applied to hydrodynamics, the proof gives a first-principle derivation of the phenomenological entropy current condition and provides a constructive procedure for obtaining the entropy current.