Theory of quantum fluctuations and the Onsager relations

A microscopic model is constructed within the theory of normal fluctuations for quantum systems, yielding an irreversible dynamics satisfying the Onsager relations. The property of return to equilibrium and the principle of minimal entropy production are proved.     

Higher Order Quantum Onsager Coefficients from Dynamical Invariants

Functionals representing dynamical invariants under unitary quantum dynamics of open systems are used to derive Onsager coefficients for entropy production in irreversible processes if the nonunitary time evolution is determined by quantum dynamical semigroups. The procedure allows a derivation from first principles of the quantum analogue to the classical case.     

The Onsager reciprocity relation and generalized efficiency of a thermal Brownian motor

Based on a general model of Brownian motors, the Onsager coefficients and generalized efficiency of a thermal Brownian motor are calculated analytically. It is found that the Onsager reciprocity relation holds and the Onsager coefficients are not affected by the kinetic energy change due to the particle's motion. Only when the heat leak in the system is negligible can the determinant of the Onsager matrix vanish. Moreover, the influence of the main parameters characterizing the model on the generalized efficiency of the Brownian motor is discussed in detail. The characteristic curves of the generalized efficiency varying with these parameters are presented, and the maximum generalized efficiency and the corresponding optimum parameters are determined. The results obtained here are of general significance. They are used to analyze the performance characteristics of the Brownian motors operating in the three interesting cases with zero heat leak, zero average drift velocity or a linear response relation, so that some important conclusions in current references are directly included in some limit cases of the present paper.     

Spectral Properties of Effective Dynamics from Conditional Expectations

The reduction of high-dimensional systems to effective models on a smaller set of variables is an essential task in many areas of science. For stochastic dynamics governed by diffusion processes, a general procedure to find effective equations is the conditioning approach. In this paper, we are interested in the spectrum of the generator of the resulting effective dynamics, and how it compares to the spectrum of the full generator. We prove a new relative error bound in terms of the eigenfunction approximation error for reversible systems. We also present numerical examples indicating that, if Kramers–Moyal (KM) type approximations are used to compute the spectrum of the reduced generator, it seems largely insensitive to the time window used for the KM estimators. We analyze the implications of these observations for systems driven by underdamped Langevin dynamics, and show how meaningful effective dynamics can be defined in this setting.     

Accelerated simulations of aromatic polymers: application to polyether ether ketone (PEEK)

For aromatic polymers, the out-of-plane oscillations of aromatic groups limit the maximum accessible time step in a molecular dynamics simulation. We present a systematic approach to removing such high-frequency oscillations from planar groups along aromatic polymer backbones, while preserving the dynamical properties of the system. We consider, as an example, the industrially important polymer, polyether ether ketone (PEEK), and show that this coarse graining technique maintains excellent agreement with the fully flexible all-atom and all-atom rigid bond models whilst allowing the time step to increase fivefold to 5 fs.     

Nonanalytic dispersion relations for classical fluids

The analytic structure of the hydrodynamic frequenciesz(k) for the sound, heat, and shear modes and of the hydrodynamic equations for a monatomic fluid are discussed on the basis of the mode-mode coupling theory. It is shown that the hydrodynamic frequencies depend on the wave numberk, for smallk, asz(k) = ak + bk ² + and that some of the correlation functions that appear in the Fourier-Laplace transforms of the hydrodynamic equations contain branch point singularities. The implications of these results for the derivation of linear hydrodynamic equations, such as the Burnett equations, and for the long-time behavior of time correlation functions are discussed.     

The 3-dimensional random walk with applications to overstretched DNA and the protein titin

We study the three-dimensional persistent random walk with drift. Then we develop a thermodynamic model that is based on this random walk without assuming the Boltzmann-Gibbs form for the equilibrium distribution. The simplicity of the model allows us to perform all calculations in closed form. We show that, despite its simplicity, the model can be used to describe different polymer stretching experiments. We study the reversible overstretching transition of DNA and the static force-extension relation of the protein titin.     

A new statistical mechanics approach to dense granular media

A new statistical mechanics approach to dense granular media is presented. The thermodynamic formalism is set out directly in terms of elastic potential energy, such that the configurational temperature (the intensive property which defines the steady state) relates to a quadratic function of the stresses (rather than other linear functions used in recent developments). Dense granular media are considered as canonical ensembles of noninteracting clusters, which can be identified with repeatable equilibrium configurations. Then, particles can be located in a new proposed phase space (conceived to separate the elastic potential energy levels). Although the importance of this paper lies in the method itself, it has been illustratively applied to the simple case of two-dimensional (2D) dense granular media (an arrangement of frictionless monodisperse elastic disks under isotropic horizontal stress compression). In this case, the temperature is directly replaced by the squared external pressure, and the packing ratio of the most probable microstate is close to the reported value of random close packing. Moreover, some interesting general conclusions arise.     

Extension of statistical replacement to systems with time-correlated fluctuations

Nonlinear systems with correlated stochastic parameters are approximated by simpler systems. This method is an extension of an earlier version of statistical replacement and statistical linearization. The extended method is applicable to systems with correlated fluctuations. We show how this general method reduces to the earlier methods in special cases.     

Reply to Comment on “Towards a large deviation theory for strongly correlated systems”

The computational study commented by Touchette opens the door to a desirable generalization of standard large deviation theory for special, though ubiquitous, correlations. We focus on three inter-related aspects: (i) numerical results strongly suggest that the standard exponential probability law is asymptotically replaced by a power-law dominant term; (ii) a subdominant term appears to reinforce the thermodynamically extensive entropic nature of q-generalized rate function; (iii) the correlations we discussed, correspond to Q-Gaussian distributions, differing from Lévy?s, except in the case of Cauchy–Lorentz distributions. Touchette has agreeably discussed point (i), but, unfortunately, points (ii) and (iii) escaped to his analysis. Claiming the absence of connection with q-exponentials is unjustified.     

Fluctuations in a one-dimensional mechanical system. I. The Euler limit

We prove the central limit theorem for the density fluctuation field of a one-dimensional mechanical system (hard rods with equal masses and lengths and elastic collisions) in the hydrodynamic limit on the Euler time scale. The limiting process is deterministic and is governed by the linearized Euler equations of the model.     

The Order Parameter of the Chiral Potts Model

An outstanding problem in statistical mechanics is the order parameter of the chiral Potts model. An elegant conjecture for this was made in 1983. It has since been successfully tested against series expansions, but there is as yet no proof of the conjecture. Here we show that if one makes a certain analyticity assumption similar to that used to derive the free energy, then one can indeed verify the conjecture. The method is based on the ‘‘broken rapidity line’’ approach pioneered by Jimbo et al. (J. Phys. A 26:2199--2210 (1993).).     

The time-local view of nonequilibrium statistical mechanics. II. Generalized Langevin equations

On a semiphenomenological level, generalized Langevin equations are usually obtained by adding a random force (RF) term to macroscopic deterministic equations assumed to be known. Here this procedure is made rigorous by conveniently redefining the RF, which is shown to be colored noise weakly correlated with the observables at earlier times due to the finite lifetime of microscopic events. Corresponding fluctuation-dissipation theorems are derived. Explicit expressions for the spectral density of the fluctuations are obtained in a particularly simple form, with the deviation of the line shape from the Lorentzian being related most explicitly to the spectral density of the RF. Well-known low-frequency expressions and the Einstein relation of (generalized) Brownian motion theory are modified so as to include lifetime effects. New sum rules are obtained relating dissipative quantities to contour integrals (in the complex frequency domain) over spectral densities or corresponding response functions. The Heisenberg dynamics of a complete set of macroobservables is shown to be equivalent to a generalized Orstein-Uhlenbeck stochastic process which is a non-Markovian process due to the lifetime effects.     

Single- and multiple-quantum cross-polarization in NMR of quadrupolar nuclei in static samples

Cross-polarization from a spin I=1/2 nucleus (e.g., ¹H) to a spin S = 3/2 nucleus (e.g., ²³Na) or a spin S = 5/2 nucleus (e.g., ²⁷A1 or ⁿO) in static powder samples is investigated. The results of conventional (single-quantum), three-quantum, and five-quantum cross-polarization experiments are presented and discussed. Based on a generalization of an existing theory of cross-polarization to quadrupolar nuclei, computer simulations are used to model the intensity and lineshape variations observed in cross-polarized NMR spectra as a function of the radio-frequency field strengths of the two simultaneous spin-locking pulses. These intensity and lineshape variations can also be understood in terms of the spin S = 3/2 or 5/2 nutation rates determined from experimental quadrupolar nutation spectra. The results of this study are intended as a preliminary step towards understanding single- and multiple-quantum cross-polarization to quadrupolar nuclei under MAS conditions and the application of these techniques to the MQMAS NMR experiment.     

Witten Laplacian Method for The Decay of Correlations

The aim of this paper is to apply direct methods to the study of integrals that appear naturally in Statistical Mechanics and Euclidean Field Theory. We provide weighted estimates leading to the exponential decay of the two-point correlation functions for certain classical convex unbounded models. The methods involve the study of the solutions of the Witten Laplacian equations associated with the Hamiltonian of the system.     

Hamiltonian and Brownian systems with long-range interactions: III. The BBGKY hierarchy for spatially inhomogeneous systems

We study the growth of correlations in systems with weak long-range interactions. Starting from the BBGKY hierarchy, we determine the evolution of the two-body correlation function by using an expansion of the solutions of the hierarchy in powers of 1/N in a proper thermodynamic limit N→+∞, where N is the number of particles. These correlations are responsible for the “collisional” evolution of the system beyond the Vlasov regime due to finite N effects. We obtain a general kinetic equation that can be applied to spatially inhomogeneous systems and that takes into account memory effects. These peculiarities are specific to systems with unshielded long-range interactions. For spatially homogeneous systems with short memory time like plasmas, we recover the classical Landau (or Lenard-Balescu) equations. An interest of our approach is to develop a formalism that remains in physical space (instead of Fourier space) and that can deal with spatially inhomogeneous systems. This enlightens the basic physics and provides novel kinetic equations with a clear physical interpretation. However, unless we restrict ourselves to spatially homogeneous systems, closed kinetic equations can be obtained only if we ignore some collective effects between particles. General exact coupled equations taking into account collective effects are also given. We use this kinetic theory to discuss the processes of violent collisionless relaxation and slow collisional relaxation in systems with weak long-range interactions. In particular, we investigate the dependence of the relaxation time with the system size N and try to provide a coherent discussion of all the numerical results obtained for these systems.     

Scattering problem with nonlocal separable potential of rank-two: Application to statistical mechanics

In this paper, we present a formulation of statistical mechanics of a thermodynamic system consisting of free particles and independent correlated pairs interacting via nonlocal potential in terms of the scattering properties. Some quantum statistical properties such as energy, heat capacity, second virial coefficient, virial pressure and quantum correction of kinetic energy are described analytically. The difference between the resolvents of the interacting and free Hamiltonians, represented as , that is associated with particle correlations is used for the evaluation of the properties. The statistical properties are related to correlated states, when making a pole expansion of the analytically continued momentum matrix element of . The present work illustrates these relations for a three-dimensional nonlocal separable potential of rank-two.     

Microscopic diagonal entropy and its connection to basic thermodynamic relations

We define a diagonal entropy (d-entropy) for an arbitrary Hamiltonian system as S_d=-∑_nρ_nnlnρ_nn with the sum taken over the basis of instantaneous energy states. In equilibrium this entropy coincides with the conventional von Neumann entropy S_n = −Trρ ln ρ. However, in contrast to S_n, the d-entropy is not conserved in time in closed Hamiltonian systems. If the system is initially in stationary state then in accord with the second law of thermodynamics the d-entropy can only increase or stay the same. We also show that the d-entropy can be expressed through the energy distribution function and thus it is measurable, at least in principle. Under very generic assumptions of the locality of the Hamiltonian and non-integrability the d-entropy becomes a unique function of the average energy in large systems and automatically satisfies the fundamental thermodynamic relation. This relation reduces to the first law of thermodynamics for quasi-static processes. The d-entropy is also automatically conserved for adiabatic processes. We illustrate our results with explicit examples and show that S_d behaves consistently with expectations from thermodynamics.