We extend the Carathéodory principle of the second law to quantum thermodynamics, where energy levels depend on macroscopic variables such as volume and magnetic field. This extension introduces the concept of quantum thermodynamic integrability (QTI), providing an alternative foundation for statistical mechanics. QTI is characterized by the path independence of work and heat within the thermodynamic manifold, locally described by energy levels and specific thermodynamic parameters. Within this framework, temperature naturally emerges as an integrating factor, enabling the derivation of both canonical and noncanonical states from the entropy integrable equations based on QTI. Notably, noncanonical states, which become particularly significant outside the thermodynamic limit, reveal the existence of informational correlations in finite-size thermodynamic systems.
We extend the Carathéodory principle of the second law to quantum thermodynamics, where energy levels depend on macroscopic variables such as volume and magnetic field. This extension introduces the concept of quantum thermodynamic integrability (QTI), providing an alternative foundation for statistical mechanics. QTI is characterized by the path independence of work and heat within the thermodynamic manifold, locally described by energy levels and specific thermodynamic parameters. Within this framework, temperature naturally emerges as an integrating factor, enabling the derivation of both canonical and noncanonical states from the entropy integrable equations based on QTI. Notably, noncanonical states, which become particularly significant outside the thermodynamic limit, reveal the existence of informational correlations in finite-size thermodynamic systems.
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.
In conventional thermodynamics, a macroscopic process is characterized by changes in thermodynamic variables such as temperature, pressure, and entropy. In quantum thermodynamics, the state of a system is described by a density operator ρ, and the entropy of the system is given by the von Neumann entropy S = -k_B Tr(ρ ln ρ). Recent theoretical investigations have suggested that quantum coherence and phase correlations can also be thermodynamically relevant. This paper introduces the concept of Quantum Thermodynamic Phase Transfer (QTPT), a formalism that treats the quantum phase φ_T as a thermodynamic variable that can change during a process. We propose a set of postulates that extend the first and second laws of thermodynamics to include a term that accounts for the work associated with changes in φ_T. The framework is illustrated with a simple two–level system coupled to a thermal bath and driven by a time–dependent phase. We derive expressions for the generalized free energy and the entropy production that include phase contributions. The implications of QTPT for quantum heat engines, quantum refrigeration, and the fundamental limits of quantum thermodynamic cycles are discussed. The potential for a Nobel–level recognition of the unification of quantum coherence with classical thermodynamic principles is highlighted.
The proper definition of entropy is fundamental to the relationship between statistical mechanics and thermodynamics. It also plays a major role in the recent debate about the validity of the concept of negative temperature. In this paper, I analyze and calculate the thermodynamic entropy for large but finite quantum mechanical systems. A special feature of this analysis is that the thermodynamic energy of a quantum system is shown to be a continuous variable, rather than being associated with discrete energy eigenvalues. Calculations of the entropy as a function of energy can be carried out with a Legendre transform of thermodynamic potentials obtained from a canonical ensemble. The resultant expressions for the entropy are able to describe equilibrium between quantum systems having incommensurate energy-level spacings. This definition of entropy preserves all required thermodynamic properties, including satisfaction of all postulates and laws of thermodynamics. It demonstrates the consistency of the concept of negative temperature with the principles of thermodynamics.
Operational quantum stochastic thermodynamics is a recently proposed theory to study the thermodynamics of open systems based on the rigorous notion of a quantum stochastic process or quantum causal model. In there, a stochastic trajectory is defined solely in terms of experimentally accessible measurement results, which serve as the basis to define the corresponding thermodynamic quantities. In contrast to this observer-dependent point of view, a `black box', which evolves unitarily and can simulate a quantum causal model, is constructed here. The quantum thermodynamics of this big isolated system can then be studied using widely accepted arguments from statistical mechanics. It is shown that the resulting definitions of internal energy, heat, work, and entropy have a natural extension to the trajectory level. The canonical choice of them coincides with the proclaimed definitions of operational quantum stochastic thermodynamics, thereby providing strong support in favour of that novel framework. However, a few remaining ambiguities in the definition of stochastic work and heat are also discovered and in light of these findings some other proposals are reconsidered. Finally, it is demonstrated that the first and second law hold for an even wider range of scenarios than previously thought, covering a large class of quantum causal models based solely on a single assumption about the initial system-bath state.
A central open question in quantum thermodynamics is the identification of thermodynamic entropy away from equilibrium. Although thermodynamic entropy coincides with the von Neumann entropy for a Gibbs state at equilibrium, the thermodynamic role of quantum coherence generated during nonequilibrium evolution remains unclear. Here, we show that von Neumann entropy does not, in general, represent the thermodynamic entropy governing heat exchange in coherent nonequilibrium quantum systems. By integrating the resource theory of quantum coherence with thermodynamic principles, we develop a general framework for nonequilibrium quantum thermodynamics. We identify thermodynamic entropy with the energy entropy derived from energy-measurement statistics and introduce a dynamical temperature extending the equilibrium concept to nonequilibrium states. Consequently, we obtain an exact entropy-balance relation separating the entropy flux associated with heat exchange from the coherence-loss contribution to entropy production, establishing an operational connection between quantum coherence, heat flow, and total entropy change. Unlike approaches relying on equilibrium reference states or stationary Gibbs ensembles, our framework uses instantaneous dynamical quantities and remains valid throughout transient nonequilibrium evolution. It provides consistent dynamical definitions of temperature, work, heat, and free energy. Applying the formalism to an exactly solvable open quantum system, we show that the first and second laws hold throughout transient evolution and that equilibrium thermodynamics emerges dynamically in the weak-coupling long-time limit. Our results establish a unified framework for coherent nonequilibrium quantum thermodynamics and suggest opportunities for controlling heat dissipation through coherence engineering in quantum thermal technologies.
We establish a rather deep relation between statistical mechanics and quantum mechanics at an imaginary time. For the quantum field theory, this implies a relation between finite temperature quantum field theory in Minkowski space and quantum field theory in Euclidean space with one compact Euclidean time direction. The quantum mechanical language being a proper formulation of statistical physics as a molecular theory is basically the study of quantum equilibrium as well as non-equilibrium systems. A quantum system found in a thermodynamic equilibrium state with an external classical system (thermostat or thermal reservoir) may be characterized by fixed values of thermodynamic parameters of the system, say, for example, temperature T , volume V and number of particles N . In this way the total energy of the thermostat is assumed to be much greater than the energy of the system. The behavior of the quantum system may be assumed to be independent of the nature of the thermostat. The most convenient object of the quantum theory to describe such non-isolated systems is the density matrix since the partition function does not determine any local thermodynamic quantities. It is for this reason that we introduced quantum mechanical and quantum statistical density matrices which are necessary to do the investigation via path integration. This enables us to make a transition to the quasi-classical approximation of quantum statistical mechanics, which, in turn, enables us to evaluate the first quantum correction to the classical Boltzmann distribution function.