Based on quantum statistical mechanics and microscopic quantum dynamics, we prove Planck's and Kelvin's principles for macroscopic systems in a general and realistic setting. We consider a hybrid quantum system that consists of the thermodynamic system, which is initially in thermal equilibrium, and the "apparatus" which operates on the former, and assume that the whole system evolves autonomously. This provides a satisfactory derivation of the second law for macroscopic systems.
Based on quantum statistical mechanics and microscopic quantum dynamics, we prove Planck's and Kelvin's principles for macroscopic systems in a general and realistic setting. We consider a hybrid quantum system that consists of the thermodynamic system, which is initially in thermal equilibrium, and the "apparatus" which operates on the former, and assume that the whole system evolves autonomously. This provides a satisfactory derivation of the second law for macroscopic systems.
We treat a quantum mechanical system with certain general properties which are expected to be common in macroscopic quantum systems. Starting from a PURE initial state (which may not describe an equilibrium) in which energy is mildly concentrated at a single value, we consider a time evolution determined by a time-dependent Hamiltonian as a model of an adiabatic operation in thermodynamics. We take a family of operations with the same procedure and various ``waiting times.'' Then the Minimum Work Principle is rigorously proved for almost all choices of the waiting time.
We construct a macroscopic thermodynamical theory that satisfies the second law of thermodynamics, based on quantum mechanics. More concretely, our macroscopic theory satisfies the following two features: (1) A macroscopic equilibrium state is expressed as a set of macroscopic variables a=(a1,⋯,aL), which represents coarse-grained values of a set of physical quantities, and (2) An adiabatic transformation from an equilibrium state a to another state a′ is possible if and only if sa≤sa′ holds. Here, sa is a real-valued function corresponding to the thermodynamical entropy, which depends only on macroscopic variables a. We show that such a macroscopic thermodynamical theory can be consistently constructed if the von-Neumann entropy of a generalized microcanonical state satisfies a generalized central limit theorem. We also show that even when the von-Neumann entropies do not satisfy the condition, a macroscopic thermodynamic-like theory with a similar structure exists, which could be at the foundations of nonequilibrium thermodynamics. Finally, we make a replica of (U,V,N) expression of thermodynamics satisfying (1) and (2), using a toy model of free particles in a box.
Classical statistical mechanics tries to derive the macroscopic properties of matter starting from the mechanical laws that rule the behaviour of single particles. To describe equilibrium states, only observables accounting for correlations among states are considered, and only systems consisting of a large number of particles are taken into account. The observables are described by continuous functions on phase space, and the states are represented by linear assignments of a number to each observable. Within the framework of the canonical ensemble, one deals with mechanical systems in thermal equilibrium with a thermal reservoir, and the equilibrium state is reached as a result of the interaction with the external world. The external world may be really external, or equally well, the unrecognized internal degrees of freedom, like in the calculation of viscosity or thermal conductivity. If really only the external world is the cause we may expect some surface dependence while an internal unrecognized degree of freedom would have a volume effect, unless the interactions are long range. The microcanonical ensemble is instead introduced to study isolated mechanical systems, and the equilibrium is viewed as a temporal average, rather than as a limit. Attention is then focused on partition functions, the theorem of equipartition of energy and an elementary theory of specific heats. In the second part, the Planck derivation of the law of black-body radiation is analysed, presenting in chronological order the Kirchhoff theorem, the Stefan law, the Wien displacement law, the Rayleigh–Jeans formula and the Planck hypothesis. Further topics discussed are the Einstein and Debye quantum models for specific heats of solids. These topics prepare the ground for the introduction of quantum statistical mechanics. The third part is, in fact, devoted to the analysis of identical particles in quantum mechanics.
To eliminate exceptions to the second law due to fluctuation phenomena, etc., the following changes are necessary. First we must state the laws of thermodynamics in terms of Gibbsian ensembles rather than of individual systems. Second we must sharpen our conception of the experimental procedure required for producing states of thermodynamic equilibrium. It will not suffice to isolate the system and wait. We must have the positive stirring action of thermal contact with a thermostat. Using the new definition of thermal equilibrium we can place statistical mechanics on a more satisfactory footing by showing that the thermostat experimental procedure leads to the canonical ensemble and maximizes v. Neumann's microscopic entropy. (Details of this proof appear in succeeding paper). Difficulties with his macroscopic definition of entropy are avoided by showing that his original microscopic definition is satisfactory when used in conjunction with a proper operational definition of thermodynamic equilibrium. In conclusion the second law of thermodynamics is derived from quantum statistics on the basis of the microscopic definition of entropy.
The second law of thermodynamics for adiabatic operations -- constraints on state transitions in closed systems under external control -- is one of the fundamental principles of thermodynamics. On the other hand, it is recently established that even pure quantum states can represent thermal equilibrium. However, pure quantum states do not satisfy the second law in that they are not passive, i.e., work can be extracted from them if arbitrary unitary operations are allowed. It therefore remains unresolved how quantum mechanics can be reconciled with thermodynamics. Here, based on our key quantum-mechanical notions of thermal equilibrium and adiabatic operations, we address the emergence of the second law for adiabatic operations in the thermodynamics limit. We first introduce infinite-observable macroscopic thermal equilibrium (iMATE); a quantum state, including pure states, is in iMATE if the expectation values of all additive observables agree with their equilibrium values. We also introduce a macroscopic operation as unitary evolution generated by a time-dependent additive Hamiltonian, which is regarded as corresponding to adiabatic operations. Employing these concepts, we show that no extensive work can be extracted from any quantum state in iMATE through any macroscopic operations. Furthermore, we introduce a quantum-mechanical form of entropy density such that it agrees with thermodynamic entropy density for any quantum state in iMATE. We then prove that for any initial state in iMATE, this entropy density cannot be decreased by any macroscopic operations, followed by a time-independent relaxation process. Our theory thus proves two different forms of the second law, by adopting macroscopically reasonable classes of observables, equilibrium states, and operations. We also discuss the time scales of macroscopic operations in these results.
Deriving the laws of thermodynamics from a microscopic picture is a central quest of statistical mechanics.This tutorial focuses on the derivation of the first and second law for isolated and open quantum systems far from equilibrium, where such foundational questions also become practically relevant for emergent nanotechnologies.The derivation is based on a microscopic definition of five essential quantities: internal energy, thermodynamic entropy, work, heat, and temperature.These definitions are shown to satisfy the phenomenological laws of nonequilibrium thermodynamics for a large class of states and processes.The consistency with previous results is demonstrated.The framework applies to multiple baths including particle transport and accounts for processes with, e.g., a changing temperature of the bath, which is determined microscopically.An integral fluctuation theorem for entropy production is satisfied.In summary, this tutorial introduces a consistent and versatile framework to understand and apply the laws of thermodynamics in the quantum regime and beyond.