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Graduate texts in physics

Thermal Equilibrium

Peter Hertel

Published Jan 1, 2017• 0 citations
Publisher
DOI
10.1007/978-3-319-58595-6_5

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We study the nature of and approach to thermal equilibrium in isolated quantum systems. An individual isolated macroscopic quantum system in a pure or mixed state is regarded as being in thermal equilibrium if all macroscopic observables assume rather sharply the values obtained from thermodynamics. Of such a system (or state) we say that it is in macroscopic thermal equilibrium (MATE). A stronger requirement than MATE is that even microscopic observables (i.e., ones referring to a small subsystem) have a probability distribution in agreement with that obtained from the micro‐canonical, or equivalently the canonical, ensemble for the whole system. Of such a system we say that it is in microscopic thermal equilibrium (MITE). The distinction between MITE and MATE is particularly relevant for systems with many‐body localization (MBL) for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. However, if we consider superpositions of energy eigenfunctions (i.e., typical wave functions ψ) in an energy shell, then for generic macroscopic systems, including those with MBL, most ψ are in both MATE and MITE. We explore here the properties of MATE and MITE and compare the two notions, thereby elaborating on ideas introduced in . image

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We consider the notion of thermal equilibrium for an individual closed macroscopic quantum system in a pure state, i.e., described by a wave function. The macroscopic properties in thermal equilibrium of such a system, determined by its wave function, must be the same as those obtained from thermodynamics, e.g., spatial uniformity of temperature and chemical potential. When this is true we say that the system is in macroscopic thermal equilibrium (MATE). Such a system may, however, not be in microscopic thermal equilibrium (MITE). The latter requires that the reduced density matrices of small subsystems be close to those obtained from the microcanonical, equivalently the canonical, ensemble for the whole system. The distinction between MITE and MATE is particularly relevant for systems with many-body localization for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. We note, however, that for generic macroscopic systems, including those with MBL, most wave functions in an energy shell are in both MATE and MITE. For a classical macroscopic system, MATE holds for most phase points on the energy surface, but MITE fails to hold for any phase point.

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Analysis of Absolute Temperature and Thermal Equilibrium: From Classical Axioms to Quantum and Statistical Frontiers

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A system, or a set of systems, is said to be in thermal equilibrium when no net flow of heat energy occurs between its constituent parts when they are connected by a path permeable to heat (a diathermal wall).1 This condition is the endpoint of a spontaneous process: if two bodies at different temperatures are brought into thermal contact, energy will flow from the higher-temperature object to the lower-temperature object until this flow ceases and the equilibrium state is achieved.3 Within a single system, thermal equilibrium is characterized by a temperature that is both spatially uniform (the same at all points) and temporally constant (unchanging over time).4 This uniformity of macroscopic properties—such as temperature and pressure—is what defines the state of the system.1 It is important to distinguish this from the broader state of thermodynamic equilibrium. Thermal equilibrium (uniform temperature) is a necessary component, but full thermodynamic equilibrium also requires mechanical equilibrium (uniform pressure) and diffusive equilibrium (uniform chemical potential).6 Systems can achieve thermal equilibrium without achieving full thermodynamic equilibrium.6 The Zeroth Law of Thermodynamics: The "Discovery" of Temperature The concept of temperature, while intuitive, requires a formal physical principle to exist as a measurable, fundamental property. This principle is the Zeroth Law of Thermodynamics. Although it was formulated and named after the First and Second Laws, its foundational role was recognized as a logical prerequisite for the entire structure of thermodynamics.8 The law states: If system A is in thermal equilibrium with system C, and system B is in thermal equilibrium with system C, then systems A and B are in thermal equilibrium with each other.1 In this construction, system C plays the role of a thermometer.13 The profound implication of this law is mathematical: it establishes thermal equilibrium as a transitive relation 9, or more formally, an equivalence relation.14 In mathematics, any equivalence relation partitioning a set of objects implies the existence of a common, scalar property shared by all members of a given equivalence class. The Zeroth Law thus proves the existence of a scalar function of state—a property we call temperature—that is common to all systems in mutual thermal equilibrium.9 The law is, therefore, the fundamental basis for defining temperature and building consistent, reproducible temperature scales.1 This axiomatic foundation also provides the logical origin for one of temperature's most critical characteristics: it is an intensive property. An intensive property is one that does not depend on the size or amount of the system.15 If a large system 'A' is in internal thermal equilibrium 6, any two parts of it, subsystems 'A1' and 'A2', must also be in thermal equilibrium with each other. By the Zeroth Law, a thermometer 'C' that is in thermal equilibrium with the whole system 'A' must also be in thermal equilibrium with 'A1' and 'A2' individually.13 The thermometer, therefore, gives the same reading for all three. This demonstrates that the temperature of a system in thermal equilibrium is the same as the temperature of any part of it.16

•Nov 14, 2025•0 citations
We study the nature of and approach to thermal equilibrium in isolated quantum systems. An individual isolated macroscopic quantum system in a pure or mixed state is regarded as being in thermal equilibrium if all macroscopic observables assume rather sharply the values obtained from thermodynamics. Of such a system (or state) we say that it is in macroscopic thermal equilibrium (MATE). A stronger requirement than MATE is that even microscopic observables (i.e., ones referring to a small subsystem) have a probability distribution in agreement with that obtained from the micro‐canonical, or equivalently the canonical, ensemble for the whole system. Of such a system we say that it is in microscopic thermal equilibrium (MITE). The distinction between MITE and MATE is particularly relevant for systems with many‐body localization (MBL) for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. However, if we consider superpositions of energy eigenfunctions (i.e., typical wave functions ψ) in an energy shell, then for generic macroscopic systems, including those with MBL, most ψ are in both MATE and MITE. We explore here the properties of MATE and MITE and compare the two notions, thereby elaborating on ideas introduced in . image
We consider the notion of thermal equilibrium for an individual closed macroscopic quantum system in a pure state, i.e., described by a wave function. The macroscopic properties in thermal equilibrium of such a system, determined by its wave function, must be the same as those obtained from thermodynamics, e.g., spatial uniformity of temperature and chemical potential. When this is true we say that the system is in macroscopic thermal equilibrium (MATE). Such a system may, however, not be in microscopic thermal equilibrium (MITE). The latter requires that the reduced density matrices of small subsystems be close to those obtained from the microcanonical, equivalently the canonical, ensemble for the whole system. The distinction between MITE and MATE is particularly relevant for systems with many-body localization for which the energy eigenfuctions fail to be in MITE while necessarily most of them, but not all, are in MATE. We note, however, that for generic macroscopic systems, including those with MBL, most wave functions in an energy shell are in both MATE and MITE. For a classical macroscopic system, MATE holds for most phase points on the energy surface, but MITE fails to hold for any phase point.
A system, or a set of systems, is said to be in thermal equilibrium when no net flow of heat energy occurs between its constituent parts when they are connected by a path permeable to heat (a diathermal wall).1 This condition is the endpoint of a spontaneous process: if two bodies at different temperatures are brought into thermal contact, energy will flow from the higher-temperature object to the lower-temperature object until this flow ceases and the equilibrium state is achieved.3 Within a single system, thermal equilibrium is characterized by a temperature that is both spatially uniform (the same at all points) and temporally constant (unchanging over time).4 This uniformity of macroscopic properties—such as temperature and pressure—is what defines the state of the system.1 It is important to distinguish this from the broader state of thermodynamic equilibrium. Thermal equilibrium (uniform temperature) is a necessary component, but full thermodynamic equilibrium also requires mechanical equilibrium (uniform pressure) and diffusive equilibrium (uniform chemical potential).6 Systems can achieve thermal equilibrium without achieving full thermodynamic equilibrium.6 The Zeroth Law of Thermodynamics: The "Discovery" of Temperature The concept of temperature, while intuitive, requires a formal physical principle to exist as a measurable, fundamental property. This principle is the Zeroth Law of Thermodynamics. Although it was formulated and named after the First and Second Laws, its foundational role was recognized as a logical prerequisite for the entire structure of thermodynamics.8 The law states: If system A is in thermal equilibrium with system C, and system B is in thermal equilibrium with system C, then systems A and B are in thermal equilibrium with each other.1 In this construction, system C plays the role of a thermometer.13 The profound implication of this law is mathematical: it establishes thermal equilibrium as a transitive relation 9, or more formally, an equivalence relation.14 In mathematics, any equivalence relation partitioning a set of objects implies the existence of a common, scalar property shared by all members of a given equivalence class. The Zeroth Law thus proves the existence of a scalar function of state—a property we call temperature—that is common to all systems in mutual thermal equilibrium.9 The law is, therefore, the fundamental basis for defining temperature and building consistent, reproducible temperature scales.1 This axiomatic foundation also provides the logical origin for one of temperature's most critical characteristics: it is an intensive property. An intensive property is one that does not depend on the size or amount of the system.15 If a large system 'A' is in internal thermal equilibrium 6, any two parts of it, subsystems 'A1' and 'A2', must also be in thermal equilibrium with each other. By the Zeroth Law, a thermometer 'C' that is in thermal equilibrium with the whole system 'A' must also be in thermal equilibrium with 'A1' and 'A2' individually.13 The thermometer, therefore, gives the same reading for all three. This demonstrates that the temperature of a system in thermal equilibrium is the same as the temperature of any part of it.16