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Physics Letters A

Quantum thermodynamics

M. Hossein Partovi

Published Jun 1, 1989• 57 citations
Publisher
DOI
10.1016/0375-9601(89)90221-1

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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.
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.