We obtain an exact Green-Kubo type linear response result for the heat current in an open system. The result is derived for classical Hamiltonian systems coupled to heat baths. Both lattice models and fluid systems are studied and several commonly used implementations of heat baths, stochastic as well as deterministic, are considered. The results are valid in arbitrary dimensions and for any system sizes. Our results are useful for obtaining the linear response transport properties of mesoscopic systems. Also we point out that for systems with anomalous heat transport, as is the case in low-dimensional systems, the use of the standard Green-Kubo formula is problematic and the open system formula should be used.
The Kubo formula describes a current as a response to an external field. In the case of heat conduction there is no such external field. We analyze why and to what extend it is nevertheless justified to describe heat conduction in modular quantum systems by the Kubo formula. Modular we call systems that may be described as consisting of weakly coupled identical subsystems. We explain in what sense this description applies to a large class of systems. Furthermore, we numerically evaluate the Kubo formula for some finite modular systems. We compare the results with data obtained from the direct …
A generalized Green-Kubo formula is derived for a quantum dissipative system of driven Brownian particle, in which the coupling between the system and the environment is linear. The structure is essentially the same as that for the generalized Green-Kubo formula for driven granular particles. It is demonstrated that the correction to the conventional Green-Kubo formula is zero for a free Brownian particle.
Recently we have introduced the microscopic response method (MRM) to compute the conductivity and Hall mobility for complex system with topological and thermal disorder, which is more convenient than the Kubo formula. We prove that for a canonical ensemble the MRM leads to the same expression as the Kubo formula. When the gradient of carrier density is small, the MRM reduces to the widely used Kubo-Greenwood formula.
Fluctuation theorem is derived for a quantum current system around a nonequilibrium steady state. It is demonstrated that the fluctuation theorem can be a part of the generalized Green-Kubo formula or a nonlinear response theory of an external field or a change of the chemical potential difference.
In this paper, we study exactly the thermal conductance for a low dimensional system represented by two coupled massive Brownian particles, both directly and via a Green-Kubo expression. Both approaches give exactly the same result. We also obtain exactly the steady state probability distribution for that system by means of time-averaging.
Currently, the most common method to calculate transport properties for materials under extreme conditions is based on the phenomenological Kubo-Greenwood method. The results of an inquiry into the justification and context of that model are summarized here. Specifically, the basis for its connection to equilibrium DFT and the assumption of static ions are discussed briefly.
The transport coefficients for a gas of smooth, inelastic hard spheres are obtained from the Boltzmann equation in the form of Green-Kubo relations. The associated time correlation functions are not simply those constructed from the fluxes of conserved densities. Instead, fluxes constructed from the reference local homogeneous distribution occur as well. The analysis exposes potential problems associated with a straightforward extension of linear response methods to granular systems.
We show that vertex corrections to the quasi-harmonic Green-Kubo theory of heat transport in insulators naturally lead to a generalisation of the expression for the conductivity that could be derived from the linearized Boltzmann equation, when the effects of the full scattering matrix are accounted for. Our results, which are obtained from the Mori-Zwanzig memory-function formalism, provide a fully ab initio derivation of the linearized Boltzmann transport equation and establish a connection between two recently proposed unified approaches to heat transport in insulating crystals and glasses.
We study the friction coefficient of a macroscopic sphere in a viscous fluid at low Reynolds number. First, Kirkwood's formula for the friction coefficient is reviewed on the basis of the Hamiltonian description of particle systems. According to this formula, the friction coefficient is expressed in terms of the stress correlation on the surface of the macroscopic sphere. Then, with the aid of large deviation theory, we relate the surface stress correlation to the stress correlation in the bulk of the fluid, where the latter is characterized by the viscosity in the Green-Kubo formula. By combi…
Green-Kubo and Einstein expressions for the transport coefficients of a fluid in a nonequilibrium steady state can be derived using the Fluctuation Theorem and by assuming the probability distribution of the time-averaged dissipative flux is Gaussian. These expressions are consistent with those obtained using linear response theory and are valid in the linear regime. It is shown that these expressions are however, not valid in the nonlinear regime where the fluid is driven far from equilibrium. We advance an argument for why these expression are only valid in the linear response, zero field li…
We derive the generalized Green-Kubo relation and an integral form of the fluctuation theorem that apply to uniformly sheared granular systems in which microscopic time-reversal symmetry is broken. The former relation provides an exact representation of nonequilibrium steady-state properties as the integral of the time-correlation function describing transient dynamics from an initial quiescent towards a final sheared steady state. We also investigate implications of the integral fluctuation theorem on the approach towards the steady state and on the possible form of the steady-state distribut…
We study the diffusion of tracers (self-diffusion) in a homogeneously cooling gas of dissipative particles, using the Green-Kubo relation and the Chapman-Enskog approach. The dissipative particle collisions are described by the coefficient of restitution $ε$ which for realistic material properties depends on the impact velocity. First, we consider self-diffusion using a constant coefficient of restitution, $ε=$const, as frequently used to simplify the analysis. Second, self-diffusion is studied for a simplified (stepwise) dependence of $ε$ on the impact velocity. Finally, diffusion is consider…
The Green-Kubo formula relates the spatial diffusion coefficient to the stationary velocity autocorrelation function. We derive a generalization of the Green-Kubo formula valid for systems with long-range or nonstationary correlations for which the standard approach is no longer valid. For the systems under consideration, the velocity autocorrelation function $\langle v(t+τ) v(t) \rangle$ asymptotically exhibits a certain scaling behavior and the diffusion is anomalous $\langle x^2(t) \rangle \simeq 2 D_νt^ν$. We show how both the anomalous diffusion coefficient $D_ν$ and exponent $ν$ can be e…
Near equilibrium, Green-Kubo relations provide microscopic expressions for macroscopic transport coefficients in terms of equilibrium correlation functions. At their core, they are based on the intimate relationship between response and fluctuations as embodied by the equilibrium fluctuation-dissipation theorem, a connection generically broken far from equilibrium. In this work, we identify a class of perturbations whose response around far-from-equilibrium steady states is linked to steady-state correlation functions via an equilibrium-like fluctuation-response equality. We then utilize this …
It is shown that the hydrodynamic modes of a dilute granular gas of inelastic hard spheres can be identified, and calculated in the long wavelength limit. Assuming they dominate at long times, formal expressions for the Navier-Stokes transport coefficients are derived. They can be expressed in a form that generalizes the Green-Kubo relations for molecular systems, and it is shown that they can also be evaluated by means of $N$-particle simulation methods. The form of the hydrodynamic modes to zeroth order in the gradients is used to detect the presence of inherent velocity correlations in the …
We present generalized Green-Kubo expressions for thermal transport coefficients $μ$ in non-conservative fluid-type systems, of the generic form, $μ$ $= μ_\infty$ $+\int^\infty_0 dt V^{-1} \av{I_ε\exp(t {\cal L}) I}_0$ where $\exp(t{\cal L})$ is a pseudo-streaming operator. It consists of a sum of an instantaneous transport coefficient $μ_\infty$, and a time integral over a time correlation function in a state of thermal equilibrium between a current $I$ and its conjugate current $I_ε$. This formula with $μ_\infty \neq 0$ and $I_ε\neq I$ covers vastly different systems, such as strongly repuls…
We have considered heat conduction in a one-dimensional mass disordered harmonic chain of $N$ particles connected to two Langevin type reservoirs at different temperatures. An exact expression for the boundary heat current-current auto-correlation function in the non-equilibrium steady state (NESS) is obtained in terms of non-equilibrium phonon Green's functions. The time integral of the correlation function gives expected result, both in non-equilibrium as well as equilibrium cases. Using the form of this correlation function we show that asymptotic system size dependence of current fluctuati…
In this paper, we propose a new derivation for the Green-Kubo relationship for the liquid-solid friction coefficient, characterizing hydrodynamic slippage at a wall. It is based on a general Langevin approach for the fluctuating wall velocity, involving a non-markovian memory kernel with vanishing time integral. The calculation highlights some subtleties of the wall-liquid dynamics, leading to superdiffusive motion of the fluctuating wall position.
Active fluids, which are driven at the microscale by non-conservative forces, are known to exhibit novel transport phenomena due to the breaking of time reversal symmetry. Recently, Epstein and Mandadapu [arXiv:1907.10041] obtained Green-Kubo relations for the full set of viscous coefficients governing isotropic chiral active fluids, including the so-called odd viscosity, invoking Onsager's regression hypothesis for the decay of fluctuations in active non-equilibrium steady states. In this Communication, we test these Green-Kubo relations using molecular dynamics simulations of a canonical mod…
We present a generalization of the Green-Kubo expressions for thermal transport coefficients $μ$ in complex fluids of the generic form, $μ= μ_\infty +\int^\infty_0 dt V^{-1} < J_ε\exp(t {\cal L}) J >_0$, i.e. a sum of an instantaneous transport coefficient $μ_\infty$, and a time integral over a time correlation function in a state of thermal equilibrium between a current $J$ and a transformed current $J_ε$. The streaming operator $\exp(t{\cal L})$ generates the trajectory of a dynamical variable $J(t) =\exp(t{\cal L}) J$ when used inside the thermal average $<...>_0$. These formulas are valid …
We have developed a Green-Kubo relation that enables accurate calculations of friction at solid-liquid interfaces directly from equilibrium molecular dynamics (MD) simulations and that provides a pathway to bypass the time-scale limitations of typical nonequilibrium MD simulations. The theory has been validated for a number of different interfaces and it is demonstrated that the liquid-solid slip is an intrinsic property of an interface. Because of the high numerical efficiency of our method, it can be used in the design of interfaces for applications in aqueous environments, such as nano- and…
A recently introduced stochastic model for fluid flow can be made Galilean invariant by introducing a random shift of the computational grid before collisions. This grid shifting procedure accelerates momentum transfer between cells and leads to a collisional contribution to transport coefficients. By resumming the Green-Kubo relations derived in a previous paper, it is shown that this collisional contribution to the transport coefficients can be determined exactly. The resummed Green-Kubo relations also show that there are no mixed kinetic-collisional contributions to the transport coefficien…
For driven Markovian dynamics on a network of (biomolecular) states, the generalized mobilities, i.e., the response of any current to changes in an external parameter, are expressed by an integral over an appropriate current-current correlation function and thus related to the generalized diffusion constants. As only input, a local detailed balance condition is required typically even valid for biomolecular systems operating deep in the non-equilibrium regime.
By combining confocal microscopy and Stress Assessment from Local Structural Anisotropy (SALSA), we directly measure stresses in 3D quiescent colloidal liquids. Our non-invasive and non-perturbative method allows us to measure forces $\lesssim$ 50 fN with a small and tunable probing volume, enabling us to resolve the stress fluctuations arising from particle thermal motions. We use the Green-Kubo relation to relate these measured stress fluctuations to the bulk Brownian viscosity at different volume fractions and comparing against simulations and conventional rheometry measurements. We demonst…
In recent years it was shown both theoretically and experimentally that in certain systems exhibiting anomalous diffusion the time and ensemble average mean squared displacement are remarkably different. The ensemble average diffusivity is obtained from a scaling Green-Kubo relation, which connects the scale invariant non-stationary velocity correlation function with the transport coefficient. Here we obtain the relation between time averaged diffusivity, usually recorded in single particle tracking experiments, and the underlying scale invariant velocity correlation function. The time average…
The Green-Kubo relation, the Einstein relation, and the fluctuation-response relation are representative universal relations among measurable quantities that are valid in the linear response regime. We provide pedagogical proofs of these universal relations for stochastic many-body systems. Through these simple proofs, we characterize the three relations as follows. The Green-Kubo relation is a direct result of the local detailed balance condition, the fluctuation-response relation represents the dynamic extension of both the Green-Kubo relation and the fluctuation relation in equilibrium stat…
A finite Green-Kubo thermal conductivity in a one-dimensional momentum conserving system was reported recently by Garrido et al [Phys. Rev. Lett., vol. 86, 5486 (2001)]. We first comment on the apparent contradiction with an earlier result of Prosen and Campbell [Phys. Rev. Lett., vol. 84, 2857 (2000)]. We then point out certain inconsistencies in their results and disagreements with our own results.
We discuss the foundations and extend the range of applicability of the widely used Kubo-Greenwood formula (KGF) for the electronic conductivity. The conductivity is derived from the current density, and only the probability amplitude rather than the transition probability is used. It is shown that the contribution to the conductivity from degenerate states in a low or zero frequency external electric field and the contribution from states near resonance with a finite frequency external field are finite. The improved conductivity expression does not include the familiar "energy conserving" del…
We consider electrophoresis of a single charged colloidal particle in a finite box with periodic boundary conditions, where added counterions and salt ions ensure charge neutrality. A systematic rescaling of the electrokinetic equations allows us to identify a minimum set of suitable dimensionless parameters, which, within this theoretical framework, determine the reduced electrophoretic mobility. It turns out that the salt-free case can, on the Mean Field level, be described in terms of just three parameters. A fourth parameter, which had previously been identified on the basis of straightfor…
The Green-Kubo relation for two models of granular gases is discussed. In the Maxwell model in any dimension, the effective temperature obtained from the Green-Kubo relation is shown to be frequency independent, and equal to the average kinetic energy, known as the granular temperature. In the second model analyzed, a mean-field granular gas, the collision rate of a particle is taken to be proportional to its velocity. The Green-Kubo relation in the high frequency limit is calculated for this model, and the effective temperature in this limit is shown to be equal to the granular temperature. T…
The Green-Kubo theory of thermal transport has long be considered incompatible with modern simulation methods based on electronic-structure theory, because it is based on such concepts as energy density and current, which are ill-defined at the quantum-mechanical level. Besides, experience with classical simulations indicates that the estimate of heat-transport coefficients requires analysing molecular trajectories that are more than one order of magnitude longer than deemed feasible using ab initio molecular dynamics. In this paper we report on recent theoretical advances that are allowing on…
For a quantum system in a steady state with a constant current of heat or particles driven by a temperature or chemical potential difference between two reservoirs attached to the system, the fluctuation theorem for the current was previously shown to lead to the Green-Kubo formula for the linear response coefficient for the current expressed in terms of the symmetrized correlation function of the current density operator. In this article, we show that for a quantum system in a steady state with a constant rate of work done on the system, the fluctuation theorem for a quantity induced in the s…
We address the question of whether transport coefficients obtained from a unitary closed system setting, i.e., the standard equilibrium Green-Kubo formula, are the same as the ones obtained from a weakly driven nonequilibrium steady-state calculation. We first derive a nonequilibrium Kubo-like expression for the steady-state diffusion constant expressed as a time-integral of either a current or a conserved density nonequilibrium correlation function. This expression has certain advantages over the equilibrium Green-Kubo formula, but is not clear if it gives the same value of the diffusion cons…
The closely related Green-Kubo and Helfand moment approaches are applied to obtain the thermal conductivity tensor of $β$-1,3,5,7-tetranitro-1,3,5,7-tetrazoctane ($β$-HMX) at $T=300$ K and $P=1$ atm from equilibrium molecular dynamics (MD) simulations. Direct application of the Green-Kubo formula exhibits slow convergence of the integrated thermal conductivity values even for long (120 ns) simulation times. To partially mitigate this slow convergence we developed a numerical procedure that involves filtering of the MD-calculated heat current. The filtering is accomplished by physically justifi…
We examine numerically the full spatio-temporal correlation functions for all hydrodynamic quantities for the random collision model introduced recently. The autocorrelation function of the heat current, through the Kubo formula, gives a thermal conductivity exponent of 1/3 in agreement with the analytical prediction and previous numerical work. Remarkably, this result depends crucially on the choice of boundary conditions: for periodic boundary conditions (as opposed to open boundary conditions with heat baths) the exponent is approximately 1/2. This is expected to be a generic feature of sys…
We provide firm convincing evidence that the energy transport in a one-dimensional gas of elastically colliding free particles of unequal masses is anomalous, i.e. the Fourier Law does not hold. Our conclusions are based on the analysis of the dependence of the heat current on the number of particles, of the internal temperature profile and on the Green-Kubo formalism.
Nature of energy transport around a critical point is studied in the Creutz cellular automaton. Fourier heat law is confirmed to hold in this model by a direct measurement of heat flow under a temperature gradient. The thermal conductivity is carefully investigated near the phase transition by the use of the Kubo formula. As the result, the thermal conductivity is found to take a finite value at the critical point contrary to some previous works. Equal-time correlation of the heat flow is also analyzed by a mean-field type approximation to investigate the temperature dependence of thermal cond…
Nonequilibrium statistical mechanics close to equilibrium is a physically satisfactory theory centered on the linear response formula of Green-Kubo. This formula results from a formal first order perturbation calculation without rigorous justification. A rigorous derivation of Fourier's law for heat conduction from the laws of mechanics remains thus a major unsolved problem. In this note we present a deterministic mechanical model of a heat-conducting chain with nontrivial interactions, where kinetic energy fluctuations at the nodes of the chain are removed. In this model the derivation of Fou…
We consider a $d$-dimensional disordered harmonic chain (DHC) perturbed by an energy conservative noise. We obtain uniform in the volume upper and lower bounds for the thermal conductivity defined through the Green-Kubo formula. These bounds indicate a positive finite conductivity. We prove also that the infinite volume homogenized Green-Kubo formula converges.
We study the Green-Kubo (GK) formula $κ(\varepsilon, ξ)$ for the heat conductivity of an infinite chain of $d$-dimensional finite systems (cells) coupled by a smooth nearest neighbour potential $\varepsilon V$. The uncoupled systems evolve according to Hamiltonian dynamics perturbed stochastically by an energy conserving noise of strength $ξ$. Noting that $κ(\varepsilon, ξ)$ exists and is finite whenever $ξ> 0$, we are interested in what happens when the strength of the noise $ξ\to 0$. For this, we start in this work by formally expanding $κ(\varepsilon, ξ)$ in a power series in $\varepsilon$,…
We study heat conduction in a harmonic crystal whose bulk dynamics is supplemented by random reversals (flips) of the velocity of each particle at a rate $λ$. The system is maintained in a nonequilibrium stationary state(NESS) by contacts with Langevin reservoirs at different temperatures. We show that the one-body and pair correlations in this system are the same (after an appropriate mapping of parameters) as those obtained for a model with self-consistent reservoirs. This is true both for the case of equal and random(quenched) masses. While the heat conductivity in the NESS of the ordered s…
Diffusive transport is characterized by a diffusivity tensor which may, in general, contain both a symmetric and an antisymmetric component. Although the latter is often neglected, we derive Green-Kubo relations showing it to be a general characteristic of random motion breaking time-reversal and parity symmetries, as encountered in chiral active matter. In analogy with the odd viscosity appearing in chiral active fluids, we term this component the odd diffusivity. We show how odd diffusivity emerges in a chiral random walk model, and demonstrate the applicability of the Green-Kubo relations t…
For classical systems driven out of equilibrium, Crooks derived a relation (the Crooks-Jarzynski relation), whose special cases include a relation (the Crooks relation) equivalent to the Kawasaki non-linear response relation. We derive a quantum extension of the Crooks-Jarzynski relation without explicitly using the principle of microreversibility. Its special cases lead to the Jarzynski equality and the standard linear response theory with a Green-Kubo formula with a canonical correlation function. We also derive a quantum extension of the Crooks relation using the principle of microreversibi…
We explore a number of explicit response formulae around the boundary driven zero range process to changes in the exit and entrance rates. In such a nonequilibrium regime kinetic (and not only thermodynamic) aspects make a difference in the response. Apart from a number of formal approaches, we illustrate a general decomposition of the linear response into entropic and frenetic contributions, the latter being realized from changes in the dynamical activity at the boundaries. In particular, in this way one obtains nonlinear modifications to the Green-Kubo relation. We end by bringing some gener…
An exact expression for the finite frequency response of open classical systems coupled to reservoirs is obtained. The result is valid for any conserved current. No assumption is made about the reservoirs apart from thermodynamic equilibrium. At non-zero frequencies, the expression involves correlation functions of boundary currents and cannot be put in the standard Green-Kubo form involving currents inside the system.
We investigate a class of anharmonic crystals in $d$ dimensions, $d\ge 1$, coupled to both external and internal heat baths of the Ornstein-Uhlenbeck type. The external heat baths, applied at the boundaries in the 1-direction, are at specified, unequal, temperatures $\tlb$ and $\trb$. The temperatures of the internal baths are determined in a self-consistent way by the requirement that there be no net energy exchange with the system in the non-equilibrium stationary state (NESS). We prove the existence of such a stationary self-consistent profile of temperatures for a finite system and show it…
Magnetohydrodynamics of strongly magnetized relativistic fluids is derived in the ideal and dissipative cases, taking into account the breaking of spatial symmetries by a quantizing magnetic field. A complete set of transport coefficients, consistent with the Curie and Onsager principles, is derived for thermal conduction, as well as shear and bulk viscosities. It is shown that in the most general case the dissipative function contains five shear viscosities, two bulk viscosities, and three thermal conductivity coefficients. We use Zubarev's non-equilibrium statistical operator method to relat…
Near field radiative heat transfer and dynamic Casimir forces are just two instances of topics of technological and fundamental interest studied via the formalism of fluctuational electrodynamics. From the perspective of experiment and simulations, it is hard to precisely control and probe such non-equilibrium situations. Fluctuations in equilibrium are easier to measure, and can typically be related to non-equilibrium response functions by Green-Kubo relations. We consider a collection of arbitrary objects in vacuum, perturbed by changing the temperature or velocity of one object. Developing …
Recent studies have revealed that the symmetry of interparticle potential plays an important role in one-dimensional heat conduction problem. Here we demonstrate that by stretching or compressing the Fermi-Pasta-Ulam-\b{eta} lattice, one can control the symmetry of the potential, and thus manipulate the decaying behavior of the heat current autocorrelation function (HCAF). In fact, stretching or compressing induces a fast decaying stage (FDS) during which the HCAF decays faster than power-law manners or in a power law manner but faster than ~t -1. The time range as well as the decay amplitude …
We have numerically studied heat conduction in a few one-dimensional momentum-conserving lattices with asymmetric interparticle interactions by the nonequilibrium heat bath method, the equilibrium Green-Kubo method, and the heat current power spectra analysis. Very strong finite-size effects are clearly observed. Such effects make the heat conduction obey a Fourier-like law in a wide range of lattice lengths. However, in yet longer lattice lengths, the heat conductivity regains its power-law divergence. Therefore the power-law divergence of the heat conductivity in the thermodynamic limit is v…
We provide a stochastic fractional diffusion equation description of energy transport through a finite one-dimensional chain of harmonic oscillators with stochastic momentum exchange and connected to Langevian type heat baths at the boundaries. By establishing an unambiguous finite domain representation of the associated fractional operator, we show that this equation can correctly reproduce equilibrium properties like Green-Kubo formula as well as non-equilibrium properties like the steady state temperature and current. In addition, this equation provides the exact time evolution of the tempe…
A linear irreversible thermodynamic framework of heat conduction in rigid conductors is introduced. The deviation from local equilibrium is characterized by a single internal variable and a current intensity factor. A general constitutive evolution equation of the current density of the internal energy is derived by introducing linear relationship between the thermodynamic forces and fluxes. The Fourier, Maxwell-Cattaneo-Vernotte, Guyer-Krumhansl, Jeffreys type and Green-Naghdi type equations of heat conduction are obtained as special cases. The universal character of the approach is demonstra…
The standard equilibrium Green-Kubo and nonequilibrium molecular dynamics (MD) methods for computing thermal transport coefficients in solids typically require relatively long simulation times and large system sizes. To this end, we revisit here the homogeneous nonequilibrium MD method by Evans [Phys. Lett. A \textbf{91}, 457 (1982)] and generalize it to many-body potentials that are required for more realistic materials modeling. We also propose a method for obtaining spectral conductivity and phonon mean free path from the simulation data. This spectral decomposition method does not require …
The linear response of an isolated, homogeneous granular fluid to small spatial perturbations is studied by methods of non-equilibrium statistical mechanics. The long wavelength linear hydrodynamic equations are obtained, with formally exact expressions for the susceptibilities and transport coefficients. The latter are given in equivalent Einstein-Helfand and Green-Kubo forms. The context of these results and their contrast with corresponding results for normal fluids are discussed.
In the hydrodynamic regime, the evolution of a stochastic lattice gas with symmetric hopping rules is described by a diffusion equation with density-dependent diffusion coefficient encapsulating all microscopic details of the dynamics. This diffusion coefficient is, in principle, determined by a Green-Kubo formula. In practice, even when the equilibrium properties of a lattice gas are analytically known, the diffusion coefficient cannot be computed except when a lattice gas additionally satisfies the gradient condition. We develop a procedure to systematically obtain analytical approximations …
