We present an exact derivation of the isobaric partition function of lattice hard rods with arbitrary nearest neighbor interactions. Free energy and all thermodynamics functions are derived accordingly and they written in a form that is a suitable for numerical implementation. As an application, we have considered lattice rods with pure hard core interactions, rods with long range gravitational attraction and finally a charged hard rods with charged boundaries (Bose gas), a model that is relevant for studying several phenomena such as charge regulation, ionic liquids near charged interfaces, and an array of charged smectic layers or lipid multilayers. In all cases, thermodynamic analysis have been done numerically using the Broyden algorithm.
We derive exact density functionals for systems of hard rods with first-neighbor interactions of arbitrary shape but limited range on a one-dimensional lattice. The size of all rods is the same integer unit of the lattice constant. The derivation, constructed from conditional probabilities in a Markov chain approach, yields the exact joint probability distribution for the positions of the rods as a functional of their density profile. For contact interaction ("sticky core model") between rods we give a lattice fundamental measure form of the density functional and present explicit results for …
The statistical thermodynamics of straight rigid rods of length $k$ on triangular lattices was developed on a generalization in the spirit of the lattice-gas model and the classical Guggenheim-DiMarzio approximation. In this scheme, the Helmholtz free energy and its derivatives were written in terms of the order parameter $δ$, which characterizes the nematic phase occurring in the system at intermediate densities. Then, using the principle of minimum free energy with $δ$ as a parameter, the main adsorption properties were calculated. Comparisons with Monte Carlo simulations and experimental da…
Moving micron scale objects are strongly coupled to each other by hydrodynamic interactions. The strength of this coupling decays as the inverse particle separation when the two objects are sufficiently far apart. It has been recently demonstrated that the reduced dimensionality of thin fluid layer gives rise to longer ranged, logarithmic coupling. Using holographic tweezers we show that microrods display both behaviors interacting like point particle in 3D at large distance and like point particles in 2D for distances shorter then their length. We derive a simple analytical expression that fi…
In a system of interacting thin rigid rods of equal length $2 \ell$ on a two-dimensional grid of lattice spacing $a$, we show that there are multiple phase transitions as the coupling strength $κ=\ell/a$ and the temperature are varied. There are essentially two classes of transitions. One corresponds to the Ising-type spontaneous symmetry breaking transition and the second belongs to less-studied phase transitions of geometrical origin. The latter class of transitions appear at fixed values of $κ$ irrespective of the temperature, whereas the critical coupling for the spontaneous symmetry break…
We study the different phases of a system of monodispersed hard rods of length $k$ on a cubic lattice using an efficient cluster algorithm which can simulate densities close to the fully-packed limit. For $k\leq 4$, the system is disordered at all densities. For $k=5,6$, we find a single density-driven transition from a disordered phase to high density layered-disordered phase in which the density of rods of one orientation is strongly suppressed, breaking the system into weakly coupled layers. Within a layer, the system is disordered. For $k \geq 7$, three density driven transitions are obser…
Thermodynamic and structural behavior of one-dimensional divalent patchy hard rods: Wertheim's first-order thermodynamic perturbation theory vs exact results
Universidad de Extremadura（埃斯特雷马杜拉大学）；Instituto de Computación Científica Avanzada (ICCAEx), Universidad de Extremadura（埃斯特雷马杜拉大学高级科学计算研究所）；University of Pannonia（潘诺尼亚大学）
We consider linear arrays of cells of volume $V_\mathrm{c}$ populated by monodisperse rods of size $σV_\mathrm{c}$, $σ=1,2,\ldots$, subject to hardcore exclusion interaction. Each rod experiences a position-dependent external potential. In one application we also examine effects of contact forces between rods. We employ two distinct methods of exact analysis with complementary strengths and different limits of spatial resolution to calculate profiles of pressure and density on mesoscopic and microscopic length scales at thermal equilibrium. One method uses density functionals and the other sta…
We predict the thermodynamic and structural behavior of solutions of long cross-linked filaments. We find that at the mean field level, the entropy of self-assembled junctions induces an effective attraction between the filaments that can result in a phase separation into a connected network, in equilibrium with a dilute phase. A connected network can also be formed in a non-thermodynamic transition upon increase of the chain, or cross link density, or with decreasing temperature. For rigid rods, at low temperatures, we predict a transition from an isotropic network, to anisotropic bundles of …
We have investigated the motion characteristics of a movable piston immersed in a one dimensional gas of hard rods by event-oriented molecular dynamics in the absence of thermal noise. Periodic and reflecting boundary conditions are explored. It is shown that the piston undergoes systematic oscillations with decaying amplitudes in short times before it comes to global thermodynamic equilibrium. Moreover, the diffusion of the piston is explored and analytical expressions for its equilibrium mean-squared displacement is obtained. It is shown that MSD of the piston does not differ much from the n…
We study the out-of-equilibrium evolution of a strongly interacting quantum spin chain which is mapped on a system of hard rods that are coherently deposited on and removed from a lattice. We show that this closed quantum system approaches an equilibrium steady state which strongly resembles a microcanonical ensemble of classical hard rods. Starting from the fully coherent evolution equation we derive a Master equation for the evolution of the number of hard rods on the lattice. This equation does not only capture properties of the equilibrium state but also describes the dynamical non-equilib…
We consider a two-dimensional lattice model for liquid crystals consisting of long rods interacting via purely hard core interactions, with two allowed orientations defined by the underlying lattice. We rigorously prove the existence of a nematic phase, i.e., we show that at intermediate densities the system exhibits orientational order, either horizontal or vertical, but no positional order. The proof is based on a two-scales cluster expansion: we first coarse grain the system on a scale comparable with the rods' length; then we express the resulting effective theory as a contour's model, whi…
In this talk I consider a two-dimensional lattice model for liquid crystals consisting of long rods interacting via purely hard core interactions, with two allowed orientations defined by the underlying lattice. I report a rigorous proof of the existence of a nematic phase: by this I mean that at intermediate densities the system exhibits orientational order, either horizontal or vertical, but no positional order. The proof is based on a two-scales cluster expansion: first the system is coarse-grained on a scale comparable with the rods' length; then the resulting effective theory is re-expres…
A Bose gas in an external potential is studied by means of the local density approximation. Analytical results are derived for the thermodynamic properties of an ideal Bose gas in a generic power-law trapping potential, and their dependence on the mutual interaction of atoms in the case of a non-ideal Bose gas.
The percolation behavior of aligned rigid rods of length $k$ ($k$-mers) on two-dimensional triangular lattices has been studied by numerical simulations and finite-size scaling analysis. The $k$-mers, containing $k$ identical units (each one occupying a lattice site), were irreversibly deposited along one of the directions of the lattice. The connectivity analysis was carried out by following the probability $R_{L,k}(p)$ that a lattice composed of $L \times L$ sites percolates at a concentration $p$ of sites occupied by particles of size $k$. The results, obtained for $k$ ranging from 2 to 80,…
We calculate the quantum corrections of the thermodynamic quantities of a system of confined Bosons at finite temperature. Systematically quantum corrections are written in a series of $\hbar$, which is convergent when $kT$ is much larger than the spacing between energy levels of the system. We apply this method to calculate analytically the thermodynamic potential of a weakly interacting Bose-gas confined in 3-d harmonic oscillator potential. For large number of particles, quantum corrections become small, and contribute to the finite size corrections to scaling.
The thermodynamic uncertainty relation sets the minimal bound of the cost-precision trade-off relation for dissipative processes. Examining the dynamics of an internally coupled system that is driven by a constant thermodynamic force, we however find that the trade-off relation of a sub-system is not constrained by the minimal bound of conventional uncertainty relation. We made our point explicit by using an exactly solvable model of interacting oscillators. As the number (N) of interacting oscillators increases, the uncertainty bound of individual oscillators is reduced to 2k_B T/N upon full …
The thermodynamic uncertainty relation (TUR) has been well studied for systems with few degrees of freedom. While, in principle, the TUR holds for more complex systems with many interacting degrees of freedom as well, little is known so far about its behavior in such systems. We analyze the TUR in the thermodynamic limit for mixtures of driven particles with short-range interactions. Our main result is an explicit expression for the optimal estimate of the total entropy production in terms of single-particle currents and correlations between two-particle currents. Quantitative results for vari…
We consider the dynamics and thermodynamics of a pair of magnetic dipoles interacting via their magnetic fields. We consider only the "spin" degrees of freedom; the dipoles are fixed in space. With this restriction it is possible to provide the general solution of the equations of motion in analytical form. Thermodynamic quantities, such as the specific heat and the zero field susceptibility are calculated by combining low temperature asymptotic series and a complete high temperature expansion. The thermal expectation value of the autocorrelation function is determined for the low temperature …
We present new integrable models of interacting spin-1/2 chains, which can be interpreted as hard rod deformations of the XXZ Heisenberg chains. The models support multiple particle types: dynamical hard rods of length $\ell$ and particles with lengths $\ell'<\ell$ that are immobile except for the interaction with the hard rods. We encounter a remarkable phenomenon in these interacting models: exact spectral degeneracies across different deformations and volumes. The algebraic integrability of these systems is also treated using a recently developed formalism for medium range integrable spin c…
We investigate the thermodynamics of simple (non-interacting) transport models beyond the scope of weak coupling. For a single fermionic or bosonic level -- tunnel-coupled to two reservoirs -- exact expressions for the stationary matter and energy current are derived from the solutions of the Heisenberg equations of motion. The positivity of the steady-state entropy production rate is demonstrated explicitly. Finally, for a configuration in which particles are pumped upwards in chemical potential by a downward temperature gradient, we demonstrate that the thermodynamic efficiency of this proce…
We investigate the interaction effect between atoms and the finite size effect of a Bose-Einstein gas at finite temperature. Using a mean field approach, we derive the thermodynamic potential on finite systems and obtain the condensate fraction, the chemical potential and the internal energy with the interaction and the finite size effects taken into account. In this approach, we can treat thermodynamic quantities as those of the ideal Bose gas. It is found that the interaction effect shifts the transition temperature by a few percent toward the lower temperature. Above the transition temperat…
We derive a model describing spatio-temporal organization of an array of microtubules interacting via molecular motors. Starting from a stochastic model of inelastic polar rods with a generic anisotropic interaction kernel we obtain a set of equations for the local rods concentration and orientation. At large enough mean density of rods and concentration of motors, the model describes an orientational instability. We demonstrate that the orientational instability leads to the formation of vortices and (for large density and/or kernel anisotropy) asters seen in recent experiments. We derive the…
We investigate the combined influence of a magnetic field and a harmonic interparticle interaction on the thermodynamic properties of a finite number of spin polarized fermions in a confiment potential. This study is an extension using our path integral approach of symmetrized density matrices for identical particles. The thermodynamical properties are calculated for a three dimensional model of N harmonically interacting spin polarized fermions in a parabolic potential well in the presence of a magnetic field. The free energy and the internal energy are obtained for a limited number of partic…
We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed single rods. The potential of mean force between the polyelectrolyte monomers yields an attractive interaction at short distances. For a range of larger values of the Bjerrum length, we find finite size poly…
The effect of nearest-neighbor coupling on the thermodynamic and dynamical properties of the ferromagnetic Hamiltonian Mean Field model (HMF) is studied. For a range of antiferromagnetic nearest-neighbor coupling, a canonical first order transition is observed, and the canonical and microcanonical ensembles are non-equivalent. In studying the relaxation time of non-equilibrium states it is found that as in the HMF model, a class of non-magnetic states is quasi-stationary, with an algebraic divergence of their lifetime with the number of degrees of freedom $N$. The lifetime of metastable states…
Systems with interacting degrees of freedom play a prominent role in stochastic thermodynamics. Our aim is to use the concept of detached path probabilities and detached entropy production for bipartite Markov processes and elaborate on a series of special cases including measurement-feedback systems, sensors and hidden Markov models. For these special cases we show that fluctuation theorems involving the detached entropy production recover known results which have been obtained separately before. Additionally, we show that the fluctuation relation for the detached entropy production can be us…
A few decades after Hill's work on nano-thermodynamics, the development of a thermodynamic framework, to account consistently for the fluctuations of small systems due to their interactions with the surrounding environment, is still underway. Here we discuss how, in a small system, the interaction energy with the environment may be described through a conjugate pair of intensive and extensive variables, giving rise to a Gibbs thermodynamics with an additional thermodynamic degree of freedom. The relevant thermodynamic potentials help describe the equilibrium conditions and the material propert…
The thermodynamic properties of two-component Fermi gases with divergent scattering length is investigated and the transition temperature for the emergence of a stable dimeric gas is obtained by a simple theoretical model where the unique property of the dimers (i.e. fermionic atom pairs) with divergent scattering length is considered. Below the transition temperature, through the investigation of the overall entropy for the mixture gas of fermionic atoms and dimers, we calculate the relation between the energy and temperature of the system. In the limit of zero temperature, based on the chemi…
Starting from the stochastic thermodynamics description of two coupled underdamped Brownian particles, we showcase and compare three different coarse-graining schemes leading to an effective thermodynamic description for the first of the two particles: marginalization over one particle, bipartite structure with information flows and the Hamiltonian of mean force formalism. In the limit of time-scale separation where the second particle with a fast relaxation time scale locally equilibrates with respect to the coordinates of the first slowly relaxing particle, the effective thermodynamics resul…
We provide a stochastic thermodynamic description across scales for $N$ identical units with all-to-all interactions that are driven away from equilibrium by different reservoirs and external forces. We start at the microscopic level with Poisson rates describing transitions between many-body states. We then identify an exact coarse graining leading to a mesoscopic description in terms of Poisson transitions between system occupations. We proceed studying macroscopic fluctuations using the Martin-Siggia-Rose formalism and large deviation theory. In the macroscopic limit ($N \to \infty$), we de…
There is a long-standing question of whether it is possible to extend the formalism of equilibrium thermodynamics to the case of non-equilibrium systems in steady states. We have made such an extension for an ideal gas in a heat flow [Hołyst \emph{et al.}, J. Chem. Phys. 157, 194108 (2022)]. Here we investigate whether such a description exists for the system with interactions: the Van der Waals gas in a heat flow. We introduce the parameters of state, each associated with a single way of changing energy. The first law of non-equilibrium thermodynamics follows from these parameters. The intern…
The approach to a substantiation of thermodynamics is offered. A conservative system of interacting elements, which is not in equilibrium, is used as a model. This system is then split into small subsystems that are accepted as being in equilibrium. Based on the D'Alambert equation for a subsystem the generalized Liouville equation is obtained. A necessary condition for irreversibility is determined. This condition is dependence the forces of interaction of subsystems on relative velocities. The equation of motion of subsystems of potentially interacting elements is obtained. The non-potential…
We show that the zeroth principle of thermodynamics applies to aging quasistationary states of long-range interacting $N$-body Hamiltonian systems. We also discuss the measurability of the temperature in these out-of-equilibrium states using a {\it short-range} interacting thermometer. As many connections are already established between such quasistationary states and nonextensive statistical mechanics, our results are the first evidence that such basic concepts apply to systems that the nonextensive formalism aims to describe.
The generalized Gibbs-Duhem equation is obtained for systems with long-range interactions in $d$ spatial dimensions. We consider that particles in the system interact through a slowly decaying pair potential of the form $1/r^ν$ with $0\leqν\leq d$. The local equation of state is obtained by computing the local entropy per particle and using the condition of local thermodynamic equilibrium. This local equation of state turns out to be that of an ideal gas. Integrating the relation satisfied by local thermodynamic variables over the volume, the equation involving global magnitudes is derived. Th…
We present the exact thermodynamics (isochores, isotherms, isobars, response functions) of a statistically interacting quantum gas in D dimensions. The results in D=1 are those of the thermodynamic Bethe ansatz for the nonlinear Schroedinger model, a gas with repulsive two-body contact potential. In all dimensions the ideal boson and fermion gases are recovered in the weak-coupling and strong-coupling limits, respectively. For all nonzero couplings ideal fermion gas behavior emerges for D>>1 and, in the limit D->infinity, a phase transition occurs at T>0. Significant deviations from ideal quan…
Some thermodynamic properties of weakly interacting Bose systems are derived from dimensional and heuristic arguments and thermodynamic relations, without resorting to statistical mechanics.
A numerical approach is presented which allows to calculate the equilibrium properties of Fermi systems which are both, strongly coupled and strongly degenerate. Based on a novel path integral representation of the many-particle density operator, quantum and spin effects are included. As an illustration, results for the pressure and energy of an electron-proton plasma are presented.
The determination of the Landau free energy (the grand thermodynamic potential) by a perturbation theory is advanced to arbitrary order for the specific case of non-interacting fermionic systems perturbed by a one-particle potential. Peculiar features of the formalism are highlighted, and its applicability for bosons is indicated. The results are employed to develop a more explicit approach describing exchange interactions between spins of Anderson's magnetic impurities in metals, semiconductors, and insulators. Within the fourth order our theory provides on the equal footing formulae for the …
Using collision driven discrete molecular dynamics (DMD), we investigate the thermodynamics and dynamics of systems of 500 dumbbell molecules interacting by a purely repulsive ramp-like discretized potential, consisting of $n$ steps of equal size. We compare the behavior of the two systems, with $n = 18$ and $n = 144$ steps. Each system exhibits both thermodynamic and dynamic anomalies, a density maximum and the translational and rotational mobilities show anomalous behavior. Starting with very dense systems and decreasing the density, both mobilities first increase, reache a maximum, then dec…
On the basis of a macroscopic ground state population it was argued recently that Bose-Einstein condensation should occur in a one-dimensional harmonic potential. We examine this situation by drawing analogies to Bosons in a two-dimensional box, where the thermodynamic limit is well-defined. We show that in both systems although the ground state populations show sharp onsets at the critical temperature, the behaviour of the specific heat is analytic, which proves the absence of a phase transition in these systems.
I demonstrate that $^4$He adsorbates in carbon nanotube materials can be treated as one-dimensional interacting gas of spinless bosons for temperatures below 8 K and for coverages such that all the adsorbates are in the groove positions of the carbon nanotube bundles. The effects of adsorbate-adsorbate interactions are studied within the scheme of virial expansion approach. The theoretical predictions for the specific heat of the interacting adsorbed gas are given.
The thermodynamic limit of the internal energy and the entropy of the system of quantum interacting particles in random medium is shown to exist under the crucial requirements of stability and temperedness of interactions. The energy turns out to be proportional to the number of particles and/or volume of the system in the thermodynamic limit. The obtained results require very general assumptions on the random one-particle model. The methods are mainly based on subadditive type inequalities.
We study the mechanical and thermodynamic properties of different traffic models for kinesin which are relevant in biological and experimental contexts. We find that motor-motor interactions play a fundamental role by enhancing the thermodynamic efficiency at maximum power of the motors, as compared to the non-interacting system, in a wide range of biologically compatible scenarios. We furthermore consider the case where the motor-motor interaction directly affects the internal chemical cycle and investigate the effect on the system dynamics and thermodynamics.
An exact closed relativistic kinetic equation is derived for a system of identical classical particles interacting with each other through a scalar field. The microscopic deterministic mechanism of the irreversible equilibration process in a relativistic classical system of interacting particles has been established. Keywords: Irreversible equilibration process; Classical relativistic dynamics; Retarded interactions.
The density-functional (DF) theory provides a simple method for calculating the properties of an interacting system under an external potential by associating it with a corresponding non-interacting system. Here, we find some relations in this non-interacting system, which can enable us to set up the thermodynamical relations for a neutral electron-nucleus mixture in terms of quantities of the non-interacting system and the exchange-correlation effect. In this way, Andersen's force theorems are clearly described and easily proved in conjunction with other types of force theorems, Janak's theor…
The standard formulation of tunneling transport rests on an open-boundary modeling. There, conserving approximations to nonequilibrium Green function or quantum-statistical mechanics provide consistent but computational costly approaches; alternatively, use of density-dependent ballistic-transport calculations [e.g., Phys. Rev. B 52, 5335 (1995)], here denoted `DBT', provide computationally efficient (approximate) atomistic characterizations of the electron behavior but has until now lacked a formal justification. This paper presents an exact, variational nonequilibrium thermodynamic theory fo…
We calculate the entropy in a trapped, resonantly interacting Fermi gas as a function of temperature for a wide range of magnetic fields between the BCS and Bose-Einstein condensation endpoints. This provides a basis for the important technique of adiabatic sweep thermometry, and serves to characterize quantitatively the evolution and nature of the excitations of the gas. The results are then used to calibrate the temperature in several ground breaking experiments on $^6$Li and $^{40}$K.
Systems of interacting fermions can give rise to ground states whose correlations become effectively free-fermion-like in the thermodynamic limit, as shown by Baxter for a class of integrable models that include the one-dimensional XYZ spin-$\frac{1}{2}$ chain. Here, we quantitatively analyse this behaviour by establishing the relation between system size and correlation length required for the fermionic Gaussianity to emerge. Importantly, we demonstrate that this behaviour can be observed through the applicability of Wick's theorem and thus it is experimentally accessible. To establish the re…
The limit n to infinity of the classical O(n) phi^4 model on a 3d film with free surfaces is studied. Its exact solution involves a self-consistent 1d Schrödinger equation, which is solved numerically for a partially discretized as well as for a fully discrete lattice model. Numerically exact results are obtained for the scaled Casimir force at all temperatures. Obtained via a single framework, they exhibit all relevant qualitative features of the thermodynamic Casimir force known from wetting experiments on Helium-4 and Monte Carlo simulations, including a pronounced minimum below the bulk cr…
