Thermodynamics dictates that the specific heat of a system is strictly non-negative. However, in finite classical systems there are well known theoretical and experimental cases where this rule is violated, in particular finite atomic clusters. Here, we show for the first time that negative heat capacity can also occur in finite quantum systems. The physical scenario on which this effect might be experimentally observed is discussed. Observing such an effect might lead to the design of new light harvesting nano devices, in particular a solar nano refrigerator.
Heat capacities of model systems with finite numbers of effective degrees of freedom are evaluated using canonical and microcanonical thermodynamics. Discrepancies between both approaches, which are observed even in the infinite-size limit, are particularly large in systems that exhibit an excited-state quantum phase transition. The corresponding irregularity of the spectrum generates a singularity in the microcanonical heat capacity and affects smoothly the canonical heat capacity.
We present a rigorous full quantum mechanical model for the lattice heat capacity of mesoscopic nanostructures in various dimensions. Model can be applied to arbitrary nanostructures with known vibrational spectrum in zero, one, two, or three dimensions. The limiting case of infinitely sized multi-dimensional materials are also found, which are in agreement with well-known results. As examples, we obtain the heat capacity of fullerenes.
Anomalous Local Heat Capacity and Bipartite Entanglement
Vienna Center for Quantum Science and Technology, Atominstitut, TU Wien（维也纳量子科学与技术中心，原子研究所，维也纳工业大学）；Center for Macroscopic Quantum States (bigQ), Department of Physics, Technical University of Denmark（宏观量子态研究中心（bigQ），物理系，丹麦技术大学）
The performances of quantum thermometry in thermal equilibrium together with the output power of certain class of quantum engines share a common characteristic: both are determined by the heat capacity of the probe or working medium. After noticing that the heat capacity of spin ensembles can be significantly modified by collective coupling with a thermal bath, we build on the above observation to investigate the respective impact of such collective effect on quantum thermometry and quantum engines. We find that the precision of the temperature estimation is largely increased at high temperatu…
Non-equilibrium systems under temperature modulation are investigated in the light of the stochastic thermodynamics. We show that, for small amplitudes of the temperature oscillations, the heat flux behaves sinusoidally with time, a result that allows the definition of the complex heat capacity. The real part of the complex heat capacity is the dynamic heat capacity, and its imaginary part is shown to be proportional to the rate of entropy production. We also show that the poles of the complex heat capacity are equal to imaginary unit multiplied by the eigenvalues of the unperturbed evolution …
Seemingly different interpretations or descriptions of Einstein's model for the heat capacity of a solid can be found in textbooks and the literature. The purpose of this note is to clarify the equivalence of the different descriptions, which all lead to the same Einstein expression for the heat capacity of a solid of N atoms.
Development of steady state thermodynamics and statistical mechanics depends crucially on our ability to develop notions of equilibrium thermodynamics for nonequilibrium steady states (NESS). The present paper considers the development of heat capacity. A modified definition is proposed which continues to maintain the same relation to steady state Shannon entropy as in equilibrium, thus providing a thermodynamically consistent treatment of NESS heat capacity.
We explore two- and three-state Markov models driven out of thermal equilibrium by non-potential forces to demonstrate basic properties of the steady heat capacity based on the concept of quasistatic excess heat. It is shown that large enough driving forces can make the steady heat capacity negative. For both the low- and high-temperature regimes we propose an approximative thermodynamic scheme in terms of "dynamically renormalized" effective energy levels.
Thermal properties of few-fermion (n < 5) systems are investigated. The dependence of the heat capacity on the topology and shape of the cavity containing the particles is analyzed. It is found that the maximum of the heat capacity, occuring at low T, discussed recently by Toutounji for a system with n = 1 fermions, is even more visible for n = 2, but fades away for n = 3 and 4. For large T, the classical behavior is obtained; however, when T -> 0, the heat capacity tends to zero exponentially, not linearly, as in macroscopic and even mesoscopic systems. The physical relevance of these results…
In [Phys. Rev. E 88, 042126 (2013)] it is stated that Tsallis distributions do not emerge from thermalization with a "bath" of finite, energy-independent, heat capacity. We report evidence for the contrary.
Using the stochastic thermodynamics, we determine the entropy production and the dynamic heat capacity of systems subject to a sinusoidally time dependent temperature, in which case the systems are permanently out of thermodynamic equilibrium inducing a continuous generation of entropy. The systems evolve in time according to a Fokker-Planck or to a Fokker-Planck-Kramers equation. Solutions of these equations, for the case of harmonic forces, are found exactly from which the heat flux, the production of entropy and the dynamic heat capacity are obtained as functions of the frequency of the tem…
The heat capacities of ice and water at ambient pressure are reexamined to build an intrinsic correlation between H2O molecular motions and the heat capacity. Based on the evolution of H2O molecular motions, a satisfactory description of the heat capacity of ice and water is provided. The heat capacity of ice is related not only to H2O molecular vibrations, but also to the molecular rotations. In water, all H2O molecular vibrations, rotations and translations contribute to the heat capacity. The molecular translational motions are found to be the main contribution to the large heat capacity of…
Calculating liquid energy and heat capacity in general form is an open problem in condensed matter physics. We develop a recent approach to liquids from the solid state by accounting for the contribution of anharmonicity and thermal expansion to liquid energy and heat capacity. We subsequently compare theoretical predictions to the experiments results of 5 commonly discussed liquids, and find a good agreement with no free fitting parameters. We discuss and compare the proposed theory to previous approaches.
It is shown that the isochoric heat capacity of dense gas, fluid and liquid decreases with increasing temperature at arbitrary values of a density for many pair interaction potentials, including bonded potentials; that a decrease of the isochoric heat capacity of the liquid with increasing temperature is related to a decrease of the interaction between the particles with increasing temperature; that a radial distribution function for nonideal dilute gas, which is independent of density, can describe a temperature dependence of the isochoric heat capacity of liquid argon; that a radial distribu…
We examine the hydrodynamic phonon spectrum of a monolayer film adsorbed on the wall of a spherical pore. Due to the boundary conditions, the monolayer film exhibits a discrete phonon spectrum. The corresponding density of states per unit frequency is thus a set of delta functions and the heat capacity exhibits Arrhenius behavior at low temperatures. At high temperatures, the heat capacity approaches the C ~ T^2 behavior of a two-dimensional monolayer film. Our results for the spherical surface film are compared to previous calculations for films confined to a cylindrical surface.
Heat engines used to output useful work have important practical significance, which, in general, operate between heat baths of infinite size and constant temperature. In this paper we study the efficiency of a heat engine operating between two finite-size heat sources with initial temperature differences. The total output work of such heat engine is limited due to the finite heat capacity of the sources. We investigate the effects of different heat capacity characteristics of the sources on the heat engine's efficiency at maximum work (EMW) in the quasi-static limit. In addition, we study the…
The constant temperature derivation, which is a model-free derivation of the Boltzmann factor, is generalized in order to develop a new simple model-free derivation of a power-law Tsallis factor based on an environment with constant heat capacity. It is shown that the integral constant T_0 appeared in the new derivation is identified with the generalized temperature T_q in Tsallis thermostatistics. A constant heat capacity environment is proposed as a one-real-parameter extension of the Boltzmann reservoir, which is a model constant temperature environment developed by J.J. Prentis et al. [Am.…
We show how to extend the concept of heat capacity to nonequilibrium systems. The main idea is to consider the excess heat released by an already dissipative system when slowly changing the environment temperature. We take the framework of Markov jump processes to embed the specific physics of small driven systems and we demonstrate that heat capacities can be consistently defined in the quasistatic limit. Away from thermal equilibrium, an additional term appears to the usual energy-temperature response at constant volume, explicitly in terms of the excess work. In linear order around an equil…
We calculate the dependence of heat capacity of a free standing thin membrane on its thickness and temperature. A remarkable fact is that for a given temperature there exists a minimum in the dependence of the heat capacity on the thickness. The ratio of the heat capacity to its minimal value for a given temperature is a universal function of the ratio of the thickness to its value corresponding to the minimum. The minimal value of the heat capacitance for given temperature is proportional to the temperature squared. Our analysis can be used, in particular, for optimizing support membranes for…
We have used the generalized two-atom ideal gas model in Tsallis statistics for the statistical description of a real gas. By comparing the heat capacity with the experimental results for the two-atom molecule gases such as N2, O2 and CO, we find that these gases appear extensive at normal temperature, but they may be nonextensive at the lower temperature. Furthermore, we study the heat capacity of the generalized many-atom gas model. We conclude that, for the many-atom gas with a high degree of freedom, a weak nonextensivity of 1-q<0 can lead to the instability.
We propose a new simple way to evaluate the effect of anharmonicity on a system's thermodynamic functions such as heat capacity. In this approach, the contribution of all potentially complicated anharmonic effects to constant-volume heat capacity is evaluated by one parameter only, the coefficient of thermal expansion. Importantly, this approach is applicable not only to crystals but also to glasses and viscous liquids. To support this proposal, we perform molecular dynamics simulations of several crystalline and amorphous solids as well as liquids, and find a good agreement between results fr…
The positivity of the heat capacity is the hallmark of thermal stability of systems in thermodynamic equilibrium. We show that this property remains valid for systems with negative derivative of energy with respect to temperature, as happens to some system described by the microcanonical ensemble. The demonstration rests on considering a trajectory on the Gibbs equilibrium surface, and its projection on the entropy-energy plane. The Gibbs equilibrium surface has the convexity property, but the projection might lack this property, leading to a negative derivative of energy with respect to tempe…
The sympathetic cooling of an initially degenerate Fermi gas by either an ideal Bose gas below $T_c$ or an ideal Boltzmann gas is investigated. It is shown that the efficiency of cooling by a Bose gas below $T_c$ is by no means reduced when its heat capacity becomes much less than that of the Fermi gas, where efficiency is measured by the decrease in the temperature of the Fermi gas per number of particles evaporated from the coolant. This contradicts the intuitive idea that an efficient coolant must have a large heat capacity. In contrast, for a Boltzmann gas a minimal value of the ratio of t…
In this paper, we make use of the exact hydrodynamic solution for the Stokes equation for the velocity of a binary ionic solution that we have recently obtained, and show that the nonequilibrium pressure in an electrolyte solution subjected to an external electric field can be not only compressive, but also divergent in the region containing the coordinate origin at which the center ion of its ion atmosphere is located. This divergent compressive pressure implies that it would be theoretically possible to locally confine the ion and also to adiabatically generate heat in the local by means of …
The excess heat capacity at glass transition temperature in two types of glass-forming systems of [xNaNO3\cdot(1-x)KNO3]60[Ca(NO3)2]40 (0 \leq x \leq 1) and Ca(NO3)2\cdotyH2O (4 \leq y \leq 13) is studied. In the former system, with the replacement of K+ cation with Na+ cation, the excess heat capacity is almost invariable around 65.1 J\cdotmol-1\cdotK-1, while the excess increases by 38.9 J\cdotmol-1\cdotK-1 with the increasing per molar H2O content in latter system. A quantitative description of the excess heat capacity is built up with the consideration of atomic and molecular translational…
We examine the SPCE and TIP5P water models to study heat capacity effects associated with the hydrophobic hydration and interaction of Xenon particles. We calculate the excess chemical potential for Xenon employing the Widom particle insertion technique. The solvation enthalpy and excess heat capacity is obtained from the temperature dependence of the chemical potentials and, alternatively, directly by Ewald summation, as well as a reaction field based method. All three different approaches provide consistent results. The reaction field method allows a separation of the individual components t…
The negative nature of the heat capacity $C_V$ of thermodynamically isolated self-gravitating systems is rediscussed in the framework of a non-extensive kinetic theory. It is found that the dependence of $C_V$ on the non-extensive parameter $q$ gives rise to a negative branch with the critical value corresponding to $q = 5/3$ ($C_V\to - \infty$).
It is shown that negative heat capacity in nanoclusters is an artifact of applying equilibrium thermodynamic formalism on a small system trapped out of equilibrium in a particular structural motif representing only part of the energetically available phase space volume. Trapping may occur in either the canonical or microcanonical ensemble, but it is unavoidable in the microcanonical. A more general consequence of trapping is that all macroscopic quantities determined for nanoclusters will depend on the initial conditions.
Using an asymptotic solution of the M-impurity thermodynamics of a dilute s-d system, the impurity energy and impurity heat capacity DeltaC(T) are derived for dilute magnetic alloys with spin 1/2 and spin 3/2 impurities. The parameters which enter DeltaC are adjusted to fit experimental data on impurity heat capacity of CuCr and LaCeAl_2. Agreement is satisfactory for CuCr, at temperatures below 1K, and good for LaCeAl_2. The magnitude of theoretical DeltaC(T) agrees with experiment and does not require scaling as in previous s-d theories. Nonlinear dependence of DeltaC(T) on impurity concentr…
The data (the speed of sound, the isobaric and isochoric heat capacities as well as the heat capacity ratio) for liquid neon presented in NIST Chemistry WebBook are analyzed. It has been shown, basing on the representation of the inverse reduced volume fluctuations, that they consist of sufficient discrepancies in the subcritical region. The correction of data in this region of the coexistence curve is evaluated using the fluctuation approach and the theory of thermodynamic similarity.
When the theorem of equipartition of energy applies to the vibrational degree of freedom within diatomic molecular gas, the bond length is usually taken as zero so that the theorem is valid. Once the bond length is taken into consideration, calculations show that the mean energy of the vibrational heat capacity will significantly deviate from the standard value near the high temperature which breaks down the bond.
Heat capacity of B2O3 glass former in a wide temperature region is described well with the intrinsic motions for non-spherical B2O3 molecules, revealing that rather than a conventional network glass former, B2O3 is a typical molecular matter in which the transition from liquid to glass in the system corresponds to the frozen of translational motions for molecules. The finding might provide an opportunity to understand the mysterious glass transition, as well as the intrinsic difference between solids and liquids.
Systems with long-range as well with short-range interactions should necessarily have a convex entropy S(E) at proper phase transitions of first order, i.e. when a separation of phases occurs. Here the microcanonical heat capacity c(E)= -\frac{(\partial S/\partial E)^2}{\partial^2S/\partial E^2} is negative. This should be observable even in macroscopic systems when energy fluctuations with the surrounding world can be sufficiently suppressed.
A simple model based on the canonical-ensemble theory is outlined for hot nuclei. The properties of the model are discussed with respect to the Fermi gas model and the breaking of Cooper pairs. The model describes well the experimental level density of deformed nuclei in various mass regions. The origin of the so-called S-shape of the heat capacity curve Cv(T) is discussed.
We present results of the experimental measurements of the isobaric heat capacity for 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane, 1-bromododecane and 1-bromo-tetradecane at normal pressure and the speed of sound and the density for 1-bromotetradecane within the temperature range 298.15--423.15~K. These data on the isobaric heat capacity and the literature-based reference data for the density and the speed of sound were used to calculate the isothermal compressibility and the inverse reduced fluctuations. Based on the comparison of the results fo…
An alternative approach to the phonon theory of liquids: An analytical study of Frenkel frequency and heat capacity as a function of pressure and temperature
We study the scaling of entanglement in low-energy states of quantum many-body models on lattices of arbitrary dimensions. We allow for unbounded Hamiltonians such that systems with bosonic degrees of freedom are included. We show that if at low enough temperatures the specific heat capacity of the model decays exponentially with inverse temperature, the entanglement in every low-energy state satisfies an area law (with a logarithmic correction). This behaviour of the heat capacity is typically observed in gapped systems. Assuming merely that the low-temperature specific heat decays polynomial…
We investigate the heat capacity of liquids through a theoretical approach based on a quasiparticle description. By interpreting the microscopic dynamics of particles in liquids in terms of quasiparticles, we suggest a simplified understanding of the number of degrees of freedom in liquids. A equivalence between hydrodynamics and U(1) gauge theory, which is newly proposed in the present paper, develops the quasiparticle description to construct a new Lagrangian which correctly reproduces the number of modes at the melting points and at the critical points. The heat capacity evaluated from this…
We have obtained by Monte Carlo NVT simulations the constant-volume excess heat capacity of square-well fluids for several temperatures, densities and potential widths. Heat capacity is a thermodynamic property much more sensitive to the accuracy of a theory than other thermodynamic quantities, such as the compressibility factor. This is illustrated by comparing the reported simulation data for the heat capacity with the theoretical predictions given by the Barker-Henderson perturbation theory as well as with those given by a non-perturbative theoretical model based on Baxter's solution of the…
Heat capacities of Na_N, N = 13, 20, 55, 135, 142, and 147, clusters have been investigated using a many-body Gupta potential and microcanonical molecular dynamics simulations. Negative heat capacities around the cluster melting-like transition have been obtained for N = 135, 142, and 147, but the smaller clusters (N = 13, 20, and 55) do not show this peculiarity. By performing a survey of the cluster potential energy landscape (PEL), it is found that the width of the distribution function of the kinetic energy and the spread of the distribution of potential energy minima (isomers), are useful…
