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arXiv:1205.4386

The breakdown of the zeroth law of thermodynamics and the definition of temperature in small quantum systems

Pei Wang

Published May 20, 2012• 0 citations
arXivHTMLPDF

Abstract

We study two small quantum systems coupled to the same reservoir which is in thermal equilibrium. By studying the particle density and the energy density in the two systems before and after they contact each other, we find that the two systems are not in thermal equilibrium with each other. Our result shows that the zeroth law of thermodynamics is broken in small quantum systems at low temperatures. Therefore, the traditional way of defining temperature fails due to the breakdown of the transitive relation of thermal equilibrium. Then we show a different way of defining temperature by attaching an auxiliary site, which plays the role of a thermometer, to the small quantum system.

DOI
10.48550/arxiv.1205.4386

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We study two small quantum systems coupled to the same reservoir which is in thermal equilibrium. By studying the particle density and the energy density in the two systems before and after they contact each other, we find that the two systems are not in thermal equilibrium with each other. Our result shows that the zeroth law of thermodynamics is broken in small quantum systems at low temperatures. Therefore, the traditional way of defining temperature fails due to the breakdown of the transitive relation of thermal equilibrium. Then we show a different way of defining temperature by attaching an auxiliary site, which plays the role of a thermometer, to the small quantum system.
Abstract Thermalization of isolated quantum systems has been studied intensively in recent years and significant progresses have been achieved. Here, we study thermalization of small quantum systems that interact with large chaotic environments under the consideration of Schrödinger evolution of composite systems, from the perspective of the zeroth law of thermodynamics. Namely, we consider a small quantum system that is brought into contact with a large environmental system; after they have relaxed, they are separated and their temperatures are studied. Our question is under what conditions the small system may have a detectable temperature that is identical with the environmental temperature. This should be a necessary condition for the small quantum system to be thermalized and to have a well-defined temperature. By using a two-level probe quantum system that plays the role of a thermometer, we find that the zeroth law is applicable to quantum chaotic systems, but not to integrable systems.
The zeroth law of thermodynamics involves a transitivity relation (pairwise between three objects) expressed either in terms of ``equal temperature'' (ET), or ``in equilibrium'' (EQ) conditions. In conventional thermodynamics conditional on vanishingly weak system-bath coupling these two conditions are commonly regarded as equivalent. In this work we show that for thermodynamics at strong coupling they are inequivalent: namely, two systems can be in equilibrium and yet have different effective temperatures. A recent result [J.-T. Hsiang and B. L. Hu, Phys. Rev. D 103, 065001 (2021) for Gaussian quantum systems shows that an effective temperature T∗{T}^{*}T∗ can be defined at all times during a system's nonequilibrium evolution, but because of the inclusion of interaction energy, after equilibration the system's T∗{T}^{*}T∗ is slightly higher than the bath temperature TB{T}_{\mathrm{B}}TB​, with the deviation depending on the coupling. A second object coupled with a different strength with an identical bath at temperature TB{T}_{\mathrm{B}}TB​ will not have the same equilibrated temperature as the first object. Thus $ET\ensuremath{\ne}EQ$ for strong coupling thermodynamics. We then investigate the conditions for dynamical equilibration for two objects 1 and 2 strongly coupled with a common bath BBB, each with a different equilibrated effective temperature. We show this is possible, and prove the existence of a generalized fluctuation-dissipation relation under this configuration. This affirms that in equilibrium is a valid and perhaps more fundamental notion which the zeroth law for quantum thermodynamics at strong coupling should be based on. Only when the system-bath coupling becomes vanishingly weak that ``temperature'' appearing in thermodynamic relations becomes universally defined and makes better physical sense.
Thermodynamics is built with the concept of equilibrium states. However, it is less clear how equilibrium thermodynamics emerges through the dynamics that follows the principle of quantum mechanics. In this paper, we develop a theory of quantum thermodynamics that is applicable for arbitrary small systems, even for single particle systems coupled with a reservoir. We generalize the concept of temperature beyond equilibrium that depends on the detailed dynamics of quantum states. We apply the theory to a cavity system and a two-level system interacting with a reservoir, respectively. The results unravels (1) the emergence of thermodynamics naturally from the exact quantum dynamics in the weak system-reservoir coupling regime without introducing the hypothesis of equilibrium between the system and the reservoir from the beginning; (2) the emergence of thermodynamics in the intermediate system-reservoir coupling regime where the Born-Markovian approximation is broken down; (3) the breakdown of thermodynamics due to the long-time non-Markovian memory effect arisen from the occurrence of localized bound states; (4) the existence of dynamical quantum phase transition characterized by inflationary dynamics associated with negative dynamical temperature. The corresponding dynamical criticality provides a border separating classical and quantum worlds. The inflationary dynamics may also relate to the origin of big bang and universe inflation. And the third law of thermodynamics, allocated in the deep quantum realm, is naturally proved.
Temperature is usually defined for physical systems at thermal equilibrium. Nevertheless one may wonder if it would be possible to attribute a meaningful notion of temperature to an arbitrary quantum state, beyond simply the thermal (Gibbs) state. In this Letter, we propose such a notion of temperature considering an operational task, inspired by the zeroth law of thermodynamics. Specifically, we define two effective temperatures for quantifying the ability of a quantum system to cool down or heat up a thermal environment. In this way we can associate an operationally meaningful notion of temperature to any quantum density matrix. We provide general expressions for these effective temperatures, for both single- and many-copy systems, establishing connections to concepts previously discussed in the literature. Finally, we consider a more sophisticated scenario where the heat exchange between the system and the thermal environment is assisted by a quantum reference frame. This leads to an effect of "coherent quantum catalysis," where the use of a coherent catalyst allows for exploiting quantum energetic coherences in the system, now leading to much colder or hotter effective temperatures. We demonstrate our findings using a two-level atom coupled to a single mode of the electromagnetic field.
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
We show how the local temperature of out-of-equilibrium, quantum electron systems can be consistently defined with the help of an external voltage and temperature probe. We determine sufficient conditions under which the temperature measured by the probe (i) is independent of details of the system-probe coupling, (ii) is equal to the temperature obtained from an independent current-noise measurement, (iii) satisfies the transitivity condition expressed by the zeroth law of thermodynamics, and (iv) is consistent with Carnot's theorem. This local temperature therefore characterizes the system in the common sense of equilibrium thermodynamics, but remains well defined even in out-of-equilibrium situations with no local equilibrium.