With the use of thermodynamics and general equilibrium conditions only, we study the entropy of a fluid in the vicinity of the critical point of the liquid-vapor phase transition. By assuming a general form for the coexistence curve in the vicinity of the critical point, we show that the functional dependence of the entropy as a function of energy and particle densities necessarily obeys the scaling form hypothesized by Widom. Our analysis allows for a discussion on the properties of the corresponding scaling function, with the interesting prediction that the critical isotherm has the same functional dependence, between the energy and particles densities, as the coexistence curve. In addition to the derivation of the expected equalities of the critical exponents, the conditions that lead to scaling also imply that while the specific heat at constant volume can diverge at the critical point, the isothermal compressibility must do so.
In this paper, heat and Carnot's working substance are defined respectively by the equations $E=3pV$ and $E=3/2pV$, relating the energy $E$, the pressure $p$ and the volume $V$ of these two corpuscular systems. The thermodynamic-kinetic theoretical analysis of their equilibrium reveals that the constraints imposed by the second law on the working substance are the consequence of the relativistic and the quantum taut constraints, respectively, $|v|\le c$ and $|ΔpΔq|\ge h$, imposed on the motion of its molecules. It is further shown that the action of these restrictions is described by the ladde…
We study the thermodynamical properties of Fermi vapors confined in a harmonic external potential. In the case of the ideal Fermi gas, we compare exact density profiles with their semiclassical approximation in the conditions of recent experiments. Then, we consider the phase-separation of a multi-component Fermi vapor. In particular, we analyze the phase-separation as a function of temperature, number of particles and scattering length. Finally, we discuss the effect of rotation on the stability and thermodynamics of the trapped vapors.
We propose a unified moving boundary problem for surface growth by electrochemical and chemical vapor deposition, which is derived from constitutive equations into which stochastic forces are incorporated. We compute the coefficients in the interface equation of motion as functions of phenomenological parameters. The equation features the Kardar-Parisi-Zhang (KPZ) non-linearity and instabilities which, depending on surface kinetics, can hinder the asymptotic KPZ scaling. Our results account for the universality and the experimental scarcity of KPZ scaling in the growth processes considered.
Anomalous behavior of water in superooled region (namely decrease of density and sharp increase of response functions at atmospheric pressure) are manly associated with either existence of liquid-liquid criticality or re-entering vapor-liquid spinodal into positive pressure. Despite different origin both scenarios introduce divergence of the response functions. We articulate in the communication that the criticality is behind water anomalies, water has normal vapor-liquid spinodal and that the re-entering feature was predicted because of curved density surface as a consequence of existence of …
This work is devoted to the consistent modeling of a three-phase mixture of a gas, a liquid and its vapor. Since the gas and the vapor are mis-cible, the mixture is subjected to a non-symmetric constraint on the volume. Adopting the Gibbs formalism, the study of the extensive equilibrium entropy of the system allows to recover the Dalton's law between the two gaseous phases. In addition, we distinguish whether phase transition occurs or not between the liquid and its vapor. The thermodynamical equilibria are described both in extensive and intensive variables. In the latter case, we focus on t…
The paper concerns the construction of a compressible liquid-vapor relaxation model which is able to capture the metastable states of the non isothermal van der Waals model as well as saturation states. Starting from the Gibbs formalism, we propose a dynamical system which complies with the second law of thermodynamics. Numerical simulations illustrate the expected behaviour of metastable states: an initial metastable condition submitted to a certain perturbation may stay in the metastable state or reaches a saturation state. The dynamical system is then coupled to the dynamics of the compress…
On the basis of the correlative method of the unsymmetrized self-consistent field that yields the account of the strong anharmonicity of the lattice vibrations, it has been calculated the temperature dependence of saturated vapor pressure of higher and smaller fullerites, from C36 up to the C96, and their thermodynamic properties along their sublimation curves. We have used the intermolecular potential of Girifalco with parameters recently calculated for these fullerenes. The calculations were accomplished up to the temperature of loss of stability (spinodal point) Ts. We compare our results w…
Derivation and thermodynamically consistent coupling of a Debye-Hückel type energy to a steric electrolyte model and application to the apparent molar volume and phase boundaries
Differential geometry is powerful tool to analyze the vapor-liquid critical point on the surface of the thermodynamic equation of state. The existence of usual condition of the critical point $\left( \partial p/\partial V\right) _{T}=0$ requires the isothermal process, but the universality of the critical point is its independence of whatever process is taken, and so we can assume $\left( \partial p/\partial T\right) _{V}=0$. The distinction between the critical point and other points on the surface leads us to further assume that the critical point is geometrically represented by zero Gaussia…
A thermodynamic expression for the analog of the canonical ensemble for nonequilibrium systems is described based on a purely information theoretical interpretation of entropy. As an application, it is shown that this nonequilibrium canonical distribution implies some important results from nonequilibrium thermodynamics, specifically, the fluctuation theorem and the Jarzynski-equality.
Among the many existing molecular models of water, the MB-pol many-body potential has emerged as a remarkably accurate model, capable of reproducing thermodynamic, structural, and dynamic properties across water's solid, liquid, and vapor phases. In this work, we assessed the performance of MB-pol with respect to an important set of properties related to vapor-liquid coexistence and interfacial behavior. Through direct coexistence classical molecular dynamics simulations at temperatures 400 K < T < 600 K, we calculated properties such as equilibrium coexistence densities, vapor-liquid interfac…
I evaluate the thermodynamic curvature $R$ for fourteen pure fluids along their liquid-vapor coexistence curves, from the critical point to the triple point, using thermodynamic input from the NIST Chemistry WebBook. In this broad overview, $R$ is evaluated in both the coexisting liquid and vapor phases. $R$ is an invariant whose magnitude $|R|$ is a measure of the size of mesoscopic organized structures in a fluid, and whose sign specifies whether intermolecular interactions are effectively attractive ($R<0$) or repulsive ($R>0$). I discuss five principles for $R$ in pure fluids: 1) near the …
A novel mathematical rigorous method to obtain the vapor-liquid equilibrium curves near the critical point has been proposed covering the cases of well-known and commonly used equations of state for real gases - Van der Waals and Dieterici, which are prototypes to determine the critical exponent value of the coexistence curves system. We explain that the critical exponent value of the vapor-liquid equilibrium curves can be regarded as the analogy to the results based on classical assumptions - mean field theory. The novelty of our method has been exposed in comparison to the standard thermodyn…
In a macroscopic (quantum or classical) Hamiltonian system, we prove the second law of thermodynamics in the forms of the minimum work principle and the law of entropy increase, under the assumption that the initial state is described by a general equilibrium distribution. Therefore the second law is a logical necessity once we accept equilibrium statistical mechanics.
Based on the foundations of thermodynamics and the equilibrium conditions for the coexistence of two phases in a magnetic Ising-like system, we show, first, that there is a critical point where the isothermal susceptibility diverges and the specific heat may remain finite, and second, that near the critical point the entropy of the system, and therefore all free energies, do obey scaling. Although we limit ourselves to such a system, we elaborate about the possibilities of finding universality, as well as the precise values of the critical exponents using thermodynamics only.
In 1893, Wien applied the first two laws of thermodynamics to blackbody radiation and derived his displacement theorem. Believing that the information from thermodynamics had been exhausted, Planck turned to statistical ideas in 1900 in order to provide a physical understanding for his experimental--data-based interpolation giving the Planck spectrum without zero-point radiation. Here we point out that the third law of thermodynamics (which was developed in the early years of the 20th century) introduces additional thermodynamic information regarding thermal radiation. The Planck spectrum for …
Starting from microscopic mechanics, we derive thermodynamic relations for heat conducting nonequilibrium steady states. The extended Clausius relation enables one to experimentally determine nonequilibrium entropy to the second order in the heat current. The associated Shannon-like microscopic expression of the entropy is suggestive. When the heat current is fixed, the extended Gibbs relation provides a unified treatment of thermodynamic forces in linear nonequilibrium regime.
We determine the impact of the Friedel oscillations on the phase behavior, critical properties and thermodynamic contours in films ($2D$) and bulk phases ($3D$). Using Expanded Wang-Landau simulations, we calculate the grand-canonical partition function and, in turn, the thermodynamic properties of systems modeled with a linear combination of the Lennard-Jones and Dzugutov potentials, weighted by a parameter $X$ ($0<X<1$). Varying $X$ allows us to control the height of the first Friedel oscillation and to provide a complete characterization of the effect of the metal-like character in the pote…
The phase diagram of the attractive hard-core Yukawa fluid derived previously [M. Robles and M. López de Haro, J. Phys. Chem. C 111, 15957 (2007)] is used to obtain the liquid-vapor coexistence curve of real water. To this end, the value of the inverse range parameter of the intermolecular potential in the Yukawa fluid is fixed so that the ratio of the density at the critical point to the liquid density at the triple point in this model coincides with the same ratio in water. Subsequently, a (relatively simple) nonlinear rescaling of the temperature is performed which allows one to obtain the …
Assuming a classical statistical system of point particles the fundamental equations of continuum thermomechanics (continuity equation, equation of motion, and energy equation) shall be derived exactly. The macroscopic state functions (density, velocity, stress, energy density, heat flux) are interpreted as expected values.
Introducing the Boltzmann distribution very early in a statistical thermodynamics course (in the spirit of Feynmann) has many didactic advantages, in particular that of easily deriving the Gibbs entropy formula. In this note, a short derivation is proposed from the fundamental postulate of statistical mechanics and basics calculations accessible to undergraduate students.
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 closed 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…
A fluctuation relation is derived to extract the order parameter function $q(x)$ in weakly ergodic systems. The relation is based on measuring and classifying entropy production fluctuations according to the value of the overlap $q$ between configurations. For a fixed value of $q$, entropy production fluctuations are Gaussian distributed allowing us to derive the quasi-FDT so characteristic of aging systems. The theory is validated by extracting the $q(x)$ in various types of glassy models. It might be generally applicable to other nonequilibrium systems and experimental small systems.
Nonequilibrium thermodynamics formalism is proposed to derive the flux of grainy (bubbles-containing) matter, emerging in a nucleation growth process. Some power and non-power limits, due to the applied potential as well as owing to basic correlations in such systems, have been discussed. Some encouragement for such a discussion comes from the fact that the nucleation and growth processes studied, and their kinetics, are frequently reported in literature as self-similar (characteristic of algebraic correlations and laws) both in basic entity (grain; bubble) size as well as time scales.
It is shown that the existence of single critical point of the fluid described by van der Waals equation of state is not the hypothesis and it is the consequence of the thermodynamic conditions of liquid-vapor phase equilibrium. It is also shown that the thermodynamic conditions of liquid-vapor phase equilibrium of the fluid give equalities to zero of first and second partial derivatives at constant temperature of pressure with respect to volume at critical point which are usual conditions of existence of critical point.
We derive the continuous canonical distribution only by requiring the extensivity of the mean energy and the multiplicative probabilistic composition rule. The derivation is independent of the thermodynamic limit and moreover it does not use the usual equal a priori probability postulate. We numerically demonstrate the implications of our derivation for the free and oscillating molecules.
A simple model is proposed for the direct correlation function (DCF) for simple fluids consisting of a hard-core contribution, a simple parametrized core correction, and a mean-field tail. The model requires as input only the free energy of the homogeneous fluid, obtained, e.g., from thermodynamic perturbation theory. Comparison to the DCF obtained from simulation of a Lennard-Jones fluid shows this to be a surprisingly good approximation for a wide range of densities. The model is used to construct a density functional theory for inhomogeneous fluids which is applied to the problem of calcula…
Homogeneous nucleation of a vapor bubble from a bulk metastable phase is studied here for the first time using the multibody dissipative particle dynamics model. The van der Waals equation of state is used to define a conservative force that describes the model fluid used in this study. Additional computational tools were developed to help visualize the vapor bubble formed in the system. Continuum thermodynamic ideas are used to help identify the bubble interface and separate particles that constitute the vapor bubble and bulk liquid regions respectively. Using this idea, the density variation…
From a non-equilibrium thermodynamical framework for transport analysis based on Onsager's Regression Hypothesis, we derive the value function first described by Dirac for isotope separation. This application of the framework is interpreted as both further validation of the transport framework and as a generalization of Dirac's value function. The framework for the analysis of transport phenomena is introduced, first. From the entropy of mixing, and in the presence of gradients in thermodynamic potentials, this framework generates a dynamical transport model from which Dirac's value function i…
In this paper we propose a novel approach to construct macroscopic balance equations and constitutive equations describing various irreversible phenomena. It is based on the general principles of non-equilibrium thermodynamics and consists of four basic steps: picking suitable state variables, choosing a strictly concave entropy function, separating entropy fluxes and production rates properly, and determining a dissipation matrix. Our approach takes the advantage of both EIT and GENERIC formalisms, and shows a direct correspondence with Levermore's moment closure hierarchies for the Boltzmann…
The phase diagram (pressure versus temperature) of the pure fluid is typically envisioned as being featureless apart from the presence of the liquid-vapor coexistence curve terminating at the critical point. However, a number of recent authors have proposed that this simple picture misses important features, such as the Widom line, the Fisher-Widom line, and the Frenkel line. In our paper we discuss another way of augmenting the pure fluid phase diagram, lines of zero thermodynamic curvature $R=0$ separating regimes of fluid solid-like behavior ($R>0$) from gas-like or liquid-like behavior ($R…
Glasses have a wide range of technological applications. The recent discovery of ultrastable glasses that are obtained by depositing the vapor of a glass-forming liquid onto the surface of a cold substrate has sparked renewed interest in the effects of confinements on physicochemical properties of liquids and glasses. Here we use molecular dynamics simulations to study the effect of substrate on thin films of a model glass-forming liquid, the Kob-Andersen binary Lennard-Jones system, and compute profiles of several thermodynamic and kinetic properties across the film. We observe that the subst…
By using canonical Monte Carlo simulation, the liquid-vapor phase diagram, surface tension, interface width, and pressure for the Mie(n,m) model fluids are calculated for six pairs of parameters $m$ and $n$. It is shown that after certain re-scaling of fluid density the corresponding states rule can be applied for the calculations of the thermodynamic properties of the Mie model fluids, and for some real substances
Based on quantum statistical mechanics and microscopic quantum dynamics, we prove Planck's and Kelvin's principles for macroscopic systems in a general and realistic setting. We consider a hybrid quantum system that consists of the thermodynamic system, which is initially in thermal equilibrium, and the "apparatus" which operates on the former, and assume that the whole system evolves autonomously. This provides a satisfactory derivation of the second law for macroscopic systems. Although the main body of the article is self-contained there are two supplemental notes on closely related topics,…
We show that within classical statistical mechanics without taking the thermodynamic limit, the most general Boltzmann factor for the canonical ensemble is a q-exponential function. The only assumption here is that microcanonical distributions have to be separable from of the total system energy, which is the prerequisite for any sensible measurement. We derive that all separable distributions are parametrized by a mathematical separation constant Q which can be related to the non-extensivity q-parameter in Tsallis distributions. We further demonstrate that nature fixes the separation constant…
A new phase field crystal (PFC) type theory is presented, which accounts for the full spectrum of solid-liquid-vapor phase transitions within the framework of a single density order parameter. Its equilibrium properties show the most quantitative features to date in PFC modelling of pure substances, and full consistency with thermodynamics in pressure-volume-temperature space is demonstrated. A method to control either the volume or the pressure of the system is also introduced. Non-equilibrium simulations show that 2 and 3-phase growth of solid, vapor and liquid can be achieved, while our for…
The equilibrium density distribution and thermodynamic properties of a Lennard-Jones fluid confined to nano-sized spherical cavities at constant chemical potential was determined using Monte Carlo simulations. The results describe both a single cavity with semipermeable walls as well as a collection of closed cavities formed at constant chemical potential. The results are compared to calculations using classical Density Functional Theory (DFT). It is found that the DFT calculations give a quantitatively accurate description of the pressure and structure of the fluid. Both theory and simulation…
The vapor-liquid equilibrium (VLE) of the Mie potential, where the dispersive exponent is constant (m = 6) while the repulsive exponent n is varied between 9 and 48, is systematically investigated by molecular simulation. For systems with planar vapor-liquid interfaces, long-range correction expressions are derived, so that interfacial and bulk properties can be computed accurately. The present simulation results are found to be consistent with the available body of literature on the Mie fluid which is substantially extended. On the basis of correlations for the considered thermodynamic proper…
We obtain macroscopic isothermal thermodynamic transformations by space-time scalings of a microscopic Hamiltonian dynamics in contact with a heat bath. The microscopic dynamics is given by a chain of anharmonic oscillators subject to a varying tension (external force) and the contact with the heat bath is modeled by independent Langevin dynamics acting on each particle. After a diffusive space-time scaling and cross-graining, the profile of volume converges to the solution of a deterministic diffusive equation with boundary conditions given by the applied tension. This defines an irreversible…
A general approach for deriving the expression of reference distribution functions by statistical thermodynamics is illustrated, and applied to the case of a magnetically confined plasma. The local equilibrium is defined by imposing the minimum entropy production, which applies only to the linear regime near a stationary thermodynamically non-equilibrium state and the maximum entropy principle under the scale invariance restrictions. This procedure may be adopted for a system subject to an arbitrary number of thermodynamic forces, however, for concreteness, we analyze, afterwords, a magnetical…
We derive Tsallis entropy, Sq, from universal thermostat independence and obtain the functional form of the corresponding generalized entropy-probability relation. Our result for finite thermostats interprets thermodynamically the subsystem temperature, T1, and the index q in terms of the temperature, T, entropy, S, and heat capacity, C of the reservoir as T1 = T exp(-S/C) and q = 1 - 1/C. In the infinite C limit, irrespective to the value of S, the Boltzmann-Gibbs approach is fully recovered. We apply this framework for the experimental determination of the original temperature of a finite th…
We obtain macroscopic adiabatic thermodynamic transformations by space-time scalings of a microscopic Hamiltonian dynamics subject to random collisions with the environment. The microscopic dynamics is given by a chain of oscillators subject to a varying tension (external force) and to collisions with external independent particles of "infinite mass". The effect of each collision is to change the sign of the velocity without changing the modulus. This way the energy is conserved by the resulting dynamics. After a diffusive space-time scaling and cross-graining, the profiles of volume and energ…
A theory for non-equilibrium systems is derived from a maximum entropy approach similar in spirit to the equilibrium theory given by Gibbs. Requiring Hamilton's principle of stationary action to be satisfied on average during a trajectory, we add constraints on the transition probability distribution which lead to a path probability of the Onsager-Machlup form. Additional constraints derived from energy and momentum conservation laws then introduce heat exchange and external driving forces into the system, with Lagrange multipliers related to the temperature and pressure of an external thermos…
The excitation-chain theory of the glass transition, proposed in an earlier publication, predicts diverging, super-Arrhenius relaxation times and, {\it via} a similarly diverging length scale, suggests a way of understanding the relations between dynamic and thermodynamic properties of glass-forming liquids. I argue here that critically large excitation chains play a role roughly analogous to that played by critical clusters in the droplet model of vapor condensation. The chains necessarily induce spatial heterogeneities in the equilibrium states of glassy systems; and these heterogeneities ma…
A framework for relativistic thermodynamics and statistical physics is built by first exploiting the symmetries between energy and momentum in the derivation of the Boltzmann distribution, then using Einstein's energy-momentum relationship to derive a PDE for the partition function. It is shown that the extended Boltzmann distribution implies the existence of an inverse four-temperature, while the form of the partition function PDE implies the existence of a quantizable field theory of classical statistics, with hints of an associated gravity like gauge theory. An adaptation of the framework i…
In the presence of feedback control by "Maxwell's demon," the second law of thermodynamics and the nonequilibrium equalities such as the Jarzynski equality need to be generalized. In this paper, we derive the generalized Jarzynski equalities for classical Hamiltonian dynamics based on the Liouville's theorem, which is the same approach as the original proof of the Jarzynski equality [Phys. Rev. Lett. 78, 2690 (1997)]. The obtained equalities lead to the generalizations of the second law of thermodynamics for the Hamiltonian systems in the presence of feedback control.
One of the most promising frameworks for understanding the anomalies of cold and supercooled water postulates the existence of two competing, interconvertible local structures. If the non-ideality in the Gibbs energy of mixing overcomes the ideal entropy of mixing of these two structures, a liquid-liquid phase transition, terminated at a liquid-liquid critical point, is predicted. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data for metastable, deeply supercooled water and simulations of molecula…
A pedagogical approach for deriving the statistical mechanical partition function, in a manner that emphasizes the key role of entropy in connecting the microscopic states to thermodynamics, is introduced. The connections between the combinatoric formula $S= k \ln W$ applied to the Gibbs construction, the Gibbs entropy, $S = -k \sum\limits_i p_i \ln p_i$, and the microcanonical entropy expression $S= k \ln Ω$ are clarified. The condition for microcanonical equilibrium, and the associated role of the entropy in the thermodynamic potential is shown to arise naturally from the postulate of equal …
The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different f…
This article presents a modeling framework for a class of multiphase chemical systems based on non-equilibrium thermodynamics. Compartmental modeling is used to establish the dynamic properties of liquid-vapor systems operating far from thermodynamic equilibrium. In addition to the bulk-phase molar/energetic dynamics, interface transport processes yield to algebraic constraints in the model description. The irreversible system is thus written as a system of Differential-Algebraic Equations (DAEs). The non-equilibrium liquid-vapor DAE system is proven to be of index one. A local stability analy…
The adsorption behavior of ions at liquid-vapor interfaces exhibits several unexpected yet generic features. In particular, energy and entropy are both minimum when the solute resides near the surface, for a variety of ions in a range of polar solvents, contrary to predictions of classical theories. Motivated by this generality, and by the simple physical ingredients implicated by computational studies, we have examined interfacial solvation in highly schematic models, which resolve only coarse fluctuations in solvent density and cohesive energy. Here we show that even such lattice gas models …
We use rigorous non-equilibrium thermodynamic arguments to prove (i) the residual entropy of any system is bounded below by the experimentally (calorimetrically) determined absolute temperature entropy, which itself is bounded below by the entropy of the corresponding equilibrium (metastable supercooled liquid) state, and (ii) the instantaneous entropy cannot drop below that of the equilibrium state. The theorems follow from the second law and the existence of internal equilibrium and refer to the thermodynamic entropy. They go beyond the calorimetric observations by Johari and Khouri [J. Chem…
We extend Expanded Wang-Landau (EWL) simulations beyond classical systems and develop the EWL method for systems modeled with a tight-binding Hamiltonian. We then apply the method to determine the partition function and thus all thermodynamic properties, including the Gibbs free energy and entropy, of the fluid phases of Si. We compare the results from quantum many-body (QMB) tight binding models, which explicitly calculate the overlap between the atomic orbitals of neighboring atoms, to those obtained with classical many-body force fields (CMB), which allow to recover the tetrahedral organiza…
Monte Carlo simulations are presented for a coarse-grained model of real quadrupolar fluids. Molecules are represented by particles interacting with Lennard-Jones forces plus the thermally averaged quadrupole-quadrupole interaction. The properties discussed include the vapor-liquid coexistence curve, the vapor pressure along coexistence, and the surface tension. The full isotherms are also accessible over a wide range of temperatures and densities. It is shown that the critical parameters (critical temperature, density, and pressure) depend almost linearly on a quadrupolar parameter $q=Q^{*4} …
One of the most promising frameworks for understanding the anomalies of cold and especially supercooled water is that of two-structure thermodynamics, in which water is viewed as a non-ideal mixture of two interconvertible local structures. The non-ideality of this mixture may give rise, at very low temperatures, to a liquid-liquid phase transition (LLPT) and a liquid-liquid critical point (LLCP), at which thermodynamic response functions diverge. Various versions of the "two-structure equation of state" (TSEOS) based on this concept have shown remarkable agreement with both experimental data …
The third law of thermodynamics has a controversial past and a number of formulations due to Planck, Einstein, and Nernst. It's most accepted version, the unattainability principle, states that "any thermodynamic process cannot reach the temperature of absolute zero by a finite number of steps and within a finite time." Although formulated in 1912, there has been no general proof of the principle, and the only evidence we have for it is that particular cooling methods become less efficient as the temperature decreases. Here we provide the first derivation of a general unattainability principle…
