Fluctuation Relation beyond Linear Response Theory

The Fluctuation Relation (FR) is an asymptotic result on the distribution of certain observables averaged over time intervals T as T goes to infinity and it is a generalization of the fluctuation--dissipation theorem to far from equilibrium systems in a steady state which reduces to the usual Green-Kubo (GK) relation in the limit of small external non conservative forces. FR is a theorem for smooth uniformly hyperbolic systems, and it is assumed to be true in all dissipative ``chaotic enough'' systems in a steady state. In this paper we develop a theory of finite time corrections to FR, needed to compare the asymptotic prediction of FR with numerical observations, which necessarily involve fluctuations of observables averaged over finite time intervals T. We perform a numerical test of FR in two cases in which non Gaussian fluctuations are observable while GK does not apply and we get a non trivial verification of FR that is independent of and different from linear response theory. Our results are compatible with the theory of finite time corrections to FR, while FR would be observably violated, well within the precision of our experiments, if such corrections were neglected.Comment: Version accepted for publication on the Journal of Statistical Physics; minor changes; two references adde

Response theory: a trajectory-based approach

We collect recent results on deriving useful response relations also for nonequilibrium systems. The approach is based on dynamical ensembles, determined by an action on trajectory space. (Anti)Symmetry under time-reversal separates two complementary contributions in the response, one entropic the other frenetic. Under time-reversal invariance of the unperturbed reference process, only the entropic term is present in the response, giving the standard fluctuation-dissipation relations in equilibrium. For nonequilibrium reference ensembles, the frenetic term contributes essentially and is responsible for new phenomena. We discuss modifications in the Sutherland-Einstein relation, the occurence of negative differential mobilities and the saturation of response. We also indicate how the Einstein relation between noise and friction gets violated for probes coupled to a nonequilibrium environment. We end with some discussion on the situation for quantum phenomena, but the bulk of the text concerns classical mesoscopic (open) systems. The choice of many simple examples is trying to make the notes pedagogical, to introduce an important area of research in nonequilibrium statistical mechanics

Coarse-grained Second Order Response Theory

While linear response theory, manifested by the fluctuation dissipation theorem, can be applied at any level of coarse graining, nonlinear response theory is fundamentally of microscopic nature. For perturbations of equilibrium systems, we develop an exact theoretical framework for analyzing the nonlinear (second order) response of coarse grained observables to time-dependent perturbations, using a path-integral formalism. The resulting expressions involve correlations of the observable with coarse grained path weights. The time symmetric part of these weights depends on the paths and perturbation protocol in a complex manner; in addition, the absence of Markovianity prevents slicing of the coarse-grained path integral. We show that these difficulties can be overcome and the response function can be expressed in terms of path weights corresponding to a single-step perturbation. This formalism thus leads to an extrapolation scheme where measuring linear responses of coarse-grained variables suffices to determine their second order response. We illustrate the validity of the formalism with an exactly solvable four-state model and the near-critical Ising model.Comment: 12 pages, 7 figure

Benchmarking two-photon absorption with CC3 quadratic response theory, and comparison with density-functional response theory

We present a detailed study of the effects of electron correlation on two-photon absorption calculated by coupled cluster quadratic response theory. The hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3 has been used to investigate the effects of electron correlation on the two-photon absorption cross sections of formaldehyde (CH2O), diacetylene (C4H2), and water (H2O). In particular, the effects of triple excitations on two-photon transition cross sections are determined for the first time. In addition, we present a detailed comparison of the coupled cluster results with those obtained from Hartree-Fock and density-functional response theories. We have investigated the local-density approximation, the pure Becke-Lee-Yang-Parr (BLYP) functional, the hybrid Becke-3-parameter-Lee-Yang-Parr (B3LYP), and the Coulomb-attenuated B3LYP (CAM-B3LYP) functionals. Our results show that the CAM-B3LYP functional, when used in conjuction with a one-particle basis-set containing diffuse functions, has much promise; however, care must still be exercised for diffuse Rydberg-type states.</p

Weakly Nonlinear AC Response: Theory and Application

We report a microscopic and general theoretical formalism for electrical response which is appropriate for both DC and AC weakly nonlinear quantum transport. The formalism emphasizes the electron-electron interaction and maintains current conservation and gauge invariance. It makes a formal connection between linear response and scattering matrix theory at the weakly nonlinear level. We derive the dynamic conductance and predict the nonlinear-nonequilibrium charge distribution. The definition of a nonlinear capacitance leads to a remarkable scaling relation which can be measured to give microscopic information about a conductor