Third Law Of Thermodynamics Research Articles

Light cone thermodynamics

We show that null surfaces defined by the outgoing and infalling wave fronts emanating from and arriving at a sphere in Minkowski spacetime have thermodynamical properties that are in strict formal correspondence with those of black hole horizons in curved spacetimes. Such null surfaces, made of pieces of light cones, are bifurcate conformal Killing horizons for suitable conformally stationary observers. They can be extremal and non-extremal depending on the radius of the shining sphere. Such conformal Killing horizons have a constant light cone (conformal) temperature, given by the standard expression in terms of the generalisation of surface gravity for conformal Killing horizons. Exchanges of conformally invariant energy across the horizon are described by a first law where entropy changes are given by $1/(4\ell_p^2)$ of the changes of a geometric quantity with the meaning of horizon area in a suitable conformal frame. These conformal horizons satisfy the zeroth to the third laws of thermodynamics in an appropriate way. In the extremal case they become light cones associated with a single event; these have vanishing temperature as well as vanishing entropy.

Quantum Horn's lemma, finite heat baths, and the third law of thermodynamics

Interactions of quantum systems with their environment play a crucial role in resource-theoretic approaches to thermodynamics in the microscopic regime. Here, we analyze the possible state transitions in the presence of "small" heat baths of bounded dimension and energy. We show that for operations on quantum systems with fully degenerate Hamiltonian (noisy operations), all possible state transitions can be realized exactly with a bath that is of the same size as the system or smaller, which proves a quantum version of Horn's lemma as conjectured by Bengtsson and Zyczkowski. On the other hand, if the system's Hamiltonian is not fully degenerate (thermal operations), we show that some possible transitions can only be performed with a heat bath that is unbounded in size and energy, which is an instance of the third law of thermodynamics. In both cases, we prove that quantum operations yield an advantage over classical ones for any given finite heat bath, by allowing a larger and more physically realistic set of state transitions.

Glass Transition, Crystallization of Glass-Forming Melts, and Entropy

A critical analysis of possible (including some newly proposed) definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann) or a conventional (and not an ideal) glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role.

Quantum thermodynamics from the nonequilibrium dynamics of open systems: Energy, heat capacity, and the third law.

In a series of papers, we intend to take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations, and the laws of thermodynamics become well defined and viable for quantum many-body systems. We first describe how an open-system nonequilibrium dynamics (ONEq) approach is different from the closed combined system+ environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed in the beginning. The linkage between the two comes from the reduced density matrix of ONEq in that stage having the same form as that of the system in the CGTs. We see the open-system approach having the advantage of dealing with nonequilibrium processes as many experiments in the near future will call for. Because it spells out the conditions of QTD's existence, it can also aid us in addressing the basic issues in quantum thermodynamics from first principles in a systematic way. We then study one broad class of open quantum systems where the full nonequilibrium dynamics can be solved exactly, that of the quantum Brownian motion of N strongly coupled harmonic oscillators, interacting strongly with a scalar-field environment. In this paper, we focus on the internal energy, heat capacity, and the third law. We show for this class of physical models, amongst other findings, the extensive property of the internal energy, the positivity of the heat capacity, and the validity of the third law from the perspective of the behavior of the heat capacity toward zero temperature. These conclusions obtained from exact solutions and quantitative analysis clearly disprove claims of negative specific heat in such systems and dispel allegations that in such systems the validity of the third law of thermodynamics relies on quantum entanglement. They are conceptually and factually unrelated issues. Entropy and entanglement will be the main theme of our second paper on this subject matter.

Molecules with Two Electronic Energy Levels: Study of Nanoparticles in the Atom‐Phonon Coupling Model Including a Surface Effect

We discuss a two‐dimensional model that leads to results which reproduce, at least qualitatively, some of the experimentally observed features of spin‐conversion compounds. The molecules of these compounds have two electronic energy levels separated by Δ. The values of the elastic constants of the springs contained in the molecules are lower in the upper level. Consequently, the phonon branches of the crystal depend on the electronic states of the molecules. The fundamental level is a low spin (LS) state and the excited one is a high spin (HS) state. We study the thermal variation of the high spin fraction, i.e., the fraction of molecules in the (HS) level by using a model of atom‐phonon coupling with a boundary effect: Δ = Δb for molecules within the bulk, and Δ = Δse < Δb for molecules on the boundary. These values are compound‐dependent, but independent of the size of the crystal. Our results qualitatively reproduce two seemingly contradictory experimental results as well as the disappearance and reappearance of the hysteresis loop that is observed when the number N of molecules of the crystal is very small. Our model explains why the width of the hysteresis loop decreases with decreasing N. We find that, for any number of molecules, the entropy of the crystal vanishes at 0 K, in accordance with the third law of thermodynamics.

Casimir and Casimir-Polder forces with dissipation from first principles

We consider Casimir-Polder and Casimir forces with finite dissipation by coupling heat baths to the dipoles introducing, this way, dissipation from 'first principles'. We derive a representation of the free energy as an integral over real frequencies, which can be viewd as an generalization of the 'remarkable formula' introduced by Ford et. al. 1985. For instance, we obtain a nonperturbative representation for the atom-atom and atom-wall interactions. We investigate several limiting cases. From the limit $T\to0$ we show that the third law of thermodynamics cannot be violated within the given approach, where the dissipation parameter cannot depend on temperature 'by construction'. We conclude, that the given approach is insufficient to resolve the thermodynamic puzzle connected with the Drude model when inserted into the Lifshitz formula. Further we consider the transition to Matsubara representation and discuss modifications of the contribution from the zeroth Matsubara frequency.

The Third Law of Thermodynamics: Phase equilibria and phase diagrams at low temperatures

Great progress has been made over the recent decades in the application of computational thermodynamics (Calphad) and theoretical methodologies (CVM) including so-called first principles approaches to modeling thermodynamic properties and the calculation of phase diagrams of materials. The aim of this paper is to call attention to considerations of the THIRD LAW OF THERMODYNAMICS when evaluating these results when applied to low temperature phase equilibria. In this effort we call attention to the essential content of the modern version of this third principle of thermodynamics using an historical and pedagogical approach. An appreciation of the constraints of the THIRD LAW is shown to be valuable in projecting possible low temperature phase fields and boundaries and predicting thermodynamically consistent phase diagram configurations as T→0 K. The ideas of Simon regarding aspects or subsystems are shown to be of paramount importance in assessing the thermodynamic properties of materials at low temperatures.

Third Law of Thermodynamics as a Single Inequality

The third law of thermodynamics in the form of the unattainability principle states that exact ground-state cooling requires infinite resources. Here we investigate the amount of non-equilibrium resources needed for approximate cooling. We consider as resource any system out of equilibrium, allowing for resources beyond the i.i.d. assumption and including the input of work as a particular case. We establish in full generality a sufficient and a necessary condition for cooling and show that for a vast class of non-equilibrium resources these two conditions coincide, providing a single necessary and sufficient criterion. Such conditions are expressed in terms of a single function playing a similar role for the third law to the one of the free energy for the second law. From a technical point of view we provide new results about concavity/convexity of certain Renyi-divergences, which might be of independent interest.

Thermal Casimir effect in Kerr spacetime with quintessence and massive gravitons

Starting from an analytical expression for the Helmholtz free energy we calculate the thermal corrections to the Casimir energy density and entropy within nearby ideal parallel plates in the vacuum of a massless scalar field. Our framework is the Kerr spacetime in the presence of quintessence and massive gravitons. The high and low temperature regimes are especially analyzed in order to distinguish the main contributions. For instance, in the high temperature regime, we show that the force between the plates is repulsive and grows with both the quintessence and the massive gravitons. Regarding the Casimir entropy, our results are in agreement with the Nernst heat theorem and therefore confirm the third law of thermodynamics in the present scenario.

Entropy Constraints in the Ground State Formation of Magnetically Frustrated Systems

A systematic modification of the entropy trajectory (\(S_\mathrm{m}(T)\)) is observed at very low temperature in magnetically frustrated systems as a consequence of the constraint (\(S_\mathrm{m}\ge 0\)) imposed by the Nernst postulate. The lack of magnetic order allows to explore and compare new thermodynamic properties by tracing the specific heat (\(C_\mathrm{m}\)) behavior down to the sub-Kelvin range. Some of the most relevant findings are: (i) a common \(C_\mathrm{m}/T|_{T\rightarrow 0} \approx 7\) J/mol K\(^2\) ‘plateau’ in at least five Yb-based very-heavy-fermions (VHF) compounds; (ii) quantitative and qualitative differences between VHF and standard non-Fermi-liquids; (iii) entropy bottlenecks governing the change of \(S_\mathrm{m}(T)\) trajectories in a continuous transition into alternative ground states. A comparative analysis of \(S_\mathrm{m}(T\rightarrow 0)\) dependencies is performed in compounds suitable for adiabatic demagnetization processes according to their \(\partial ^2 S_\mathrm{m}/\partial T^2\) derivatives.

Exponential bound in the quest for absolute zero.

In most studies for the quantification of the third law of thermodynamics, the minimum temperature which can be achieved with a long but finite-time process scales as a negative power of the process duration. In this article, we use our recent complete solution for the optimal control problem of the quantum parametric oscillator to show that the minimum temperature which can be obtained in this system scales exponentially with the available time. The present work is expected to motivate further research in the active quest for absolute zero.

A Third-Law Isentropic Analysis of a Simulated Hurricane

Abstract The moist-air entropy can be used to analyze and better understand the general circulation of the atmosphere or convective motions. Isentropic analyses are commonly based on studies of different equivalent potential temperatures, all of which are assumed to fully represent the entropy of moist air. It is, however, possible to rely either on statistical physics or the third law of thermodynamics when defining and computing the absolute entropy of moist air and to study the corresponding third-law potential temperature, which is different from the previous ones. The third law assumes that the entropy for the most stable crystalline state of all substances is zero when approaching absolute zero temperature. This paper shows that the way all these moist-air potential temperatures are defined has a large impact on (i) the plotting of the isentropes for a simulation of Hurricane Dumile, (ii) the changes in moist-air entropy computed for a steam cycle defined for this hurricane, (iii) the analyses of isentropic streamfunctions computed for this hurricane, and (iv) the computations of the heat input, the work function, and the efficiency defined for this steam cycle. The moist-air entropy is a state function and the isentropic analyses must be completely determined by the local moist-air conditions. The large differences observed between the different formulations of moist-air entropy are interpreted as proof that the isentropic analyses of moist-air atmospheric motions must be achieved by using the third-law potential temperature defined from general thermodynamics.

Quantum Heat Engine and Negative Boltzmann Temperature**Support from the National Science Foundation of China under Grants Nos. 11375012, 11534002, and The Recruitment Program ofGlobal Youth Experts of China

To clarify the ambiguity on negative Boltzmann temperature in literature, we study the Carnot and the Otto cycle with one of the heat reservoirs at the negative Boltzmann temperature based on a canonical ensemble description. The work extraction, entropy production and the efficiency of these cycles are explored. Conditions for constructing and properties of these thermodynamic cycles are elucidated. We find that the apparent “violation” of the second law of thermodynamics in these cycles are due to the fact that the traditional definition of thermodynamic efficiency is inappropriate in this situation. When properly understanding the efficiency and the adiabatic processes, in which the system crosses over “absolute ZERO” in a limit sense, the Carnot cycle with one of the heat reservoirs at a negative Boltzmann temperature can be understood straightforwardly, and it contradicts neither the second nor the third law of thermodynamics. Hence, negative Boltzmann temperature is a consistent concept in thermodynamics. We use a two-level system and an Ising spin system to illustrate our central results.

Role of entropy in the ground state formation of frustrated systems

The absence of magnetic order in Rare Earth-based frustrated compounds allows to recognize the action of the third law of thermodynamics in the low temperature behavior of those systems. One of the most relevant findings is the appearance of a coincident specific heat Cm/T|T→0≈7J/molK2 ‘plateau’ in six Yb systems. This characteristic feature occurs after a systematic modification of the thermal trajectory of their entropies Sm(T) in the range of a few hundred milikelvin degrees. Such behavior is explained by the formation of an entropy-bottleneck imposed by the third law constraint (Sm|T→0≥0), that drives the system into alternative ground states. Based in these finding, three possible approaches to the Sm|T→0 limit observed in real systems are analyzed in terms of the ∂2Sm/∂T2 dependencies.

Information entropy and thermal entropy: apples and oranges

The frequent misunderstanding of information entropy is pointed out. It is shown that, contrary to fortuitous situations and common beliefs, there is no general interrelation between the information entropy and the thermodynamical entropy. We point out that the change of information entropy during measurement is determined by the resolution of the measurement instrument and these changes do not have a general and clear-cut interrelation with the change of thermal entropy. Moreover, these changes can be separated in space and time. We show classical physical considerations and examples to support this conclusion. Finally, we show that information entropy can violate the Third Law of Thermodynamics which is another indication of major differences from thermal entropy.

Cosmic censorship conjecture in Kerr-Sen black hole

The validity of the cosmic censorship conjecture for the Kerr-Sen black hole, which is a solution to the low-energy effective field theory for four-dimensional heterotic string theory, is investigated using charged particle absorption. When the black hole absorbs the particle, the charge on it changes owing to the conserved quantities of the particle. Changes in the black hole are constrained to the equation for the motion of the particle and are consistent with the laws of thermodynamics. Particle absorption increases the mass of the Kerr-Sen black hole to more than that of the absorbed charges such as angular momentum and electric charge; hence, the black hole cannot be overcharged. In the near-extremal black hole, we observe a violation of the cosmic censorship conjecture for the angular momentum in the first order of expansion and the electric charge in the second order. However, considering an adiabatic process carrying the conserved quantities as those of the black hole, we prove the stability of the black hole horizon. Thus, we resolve the violation. This is consistent with the third law of thermodynamics.

Masanes and Oppenheim on the Third Law of Thermodynamics

Masanes and Oppenheim on the Third Law of Thermodynamics

Thermodynamic constraints on the amplitude of quantum oscillations

Magneto-quantum oscillation experiments in high temperature superconductors show a strong thermally-induced suppression of the oscillation amplitude approaching critical dopings---in support of a quantum critical origin of their phase diagrams. We suggest that, in addition to a thermodynamic mass enhancement, these experiments may directly indicate the increasing role of quantum fluctuations that suppress the oscillation amplitude through inelastic scattering. We show that the traditional theoretical approaches beyond Lifshitz-Kosevich to calculate the oscillation amplitude in correlated metals result in a contradiction with the third law of thermodynamics and suggest a way to rectify this problem.

A general derivation and quantification of the third law of thermodynamics

The most accepted version of the third law of thermodynamics, the unattainability principle, states that any process cannot reach absolute zero temperature in a finite number of steps and within a finite time. Here, we provide a derivation of the principle that applies to arbitrary cooling processes, even those exploiting the laws of quantum mechanics or involving an infinite-dimensional reservoir. We quantify the resources needed to cool a system to any temperature, and translate these resources into the minimal time or number of steps, by considering the notion of a thermal machine that obeys similar restrictions to universal computers. We generally find that the obtainable temperature can scale as an inverse power of the cooling time. Our results also clarify the connection between two versions of the third law (the unattainability principle and the heat theorem), and place ultimate bounds on the speed at which information can be erased.

Proof of Nernst heat theorem and its corollaries

It is known that the Nernst’s Heat Theorem (the Third Law of Thermodynamics) having a vast number of applications was derived experimentally. In this work its theoretical proof is given outside the framework of quantum mechanical considerations using the dependence determined by R. Clausius to calculate the infinitesimal quantity of heat.