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Irreversibility and dynamical response

David T. Limmer

Published Aug 1, 2024• 0 citations
Publisher

Abstract

Abstract We have previously developed this framework in the context of static response, here we will generalize this perspective to dynamic response, and the evolution between distinct thermal equilibrium states. Of particular importance will be the derivation of the fluctuation-dissipation theorem, which relates the response of a system to its time dependent fluctuations, clarifying an equivalence between how a system responds to a small perturbation and how it regresses back to equilibrium in the absence of a perturbation. With this framework we can develop linear models of relaxation, classically and quantum mechanically, and derive equa- tions of motion suitable for describing the dynamics of thermal ensembles held at fixed temperature rather than fixed energy. These models are Gaussian, and approximate the dynamical correlations of interacting systems. These effective equations of motion are rendered stochastic due to the incomplete description of the microscopic degrees of freedom that evolve the system.

DOI
10.1093/oso/9780198919858.003.0007

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Abstract We have previously developed this framework in the context of static response, here we will generalize this perspective to dynamic response, and the evolution between distinct thermal equilibrium states. Of particular importance will be the derivation of the fluctuation-dissipation theorem, which relates the response of a system to its time dependent fluctuations, clarifying an equivalence between how a system responds to a small perturbation and how it regresses back to equilibrium in the absence of a perturbation. With this framework we can develop linear models of relaxation, classically and quantum mechanically, and derive equa- tions of motion suitable for describing the dynamics of thermal ensembles held at fixed temperature rather than fixed energy. These models are Gaussian, and approximate the dynamical correlations of interacting systems. These effective equations of motion are rendered stochastic due to the incomplete description of the microscopic degrees of freedom that evolve the system.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
We have given in two previous chapters a first introduction to non-equilibrium phenomena. The present chapter is devoted to a presentation of more general approaches, in which time dependence will be made explicit, whereas in practice we had to limit ourselves to stationary situations in Chapters 6 and 8. In the first part of the chapter, we examine the relaxation toward equilibrium of a system that has been brought out of equilibrium by an external perturbation. The main result is that, for small deviations from equilibrium, this relaxation is described by equilibrium time correlation functions, called Kubo (or relaxation) functions: this result is also known as ‘Onsager's regression law’. The Kubo functions turn out to be basic objects of non-equilibrium statistical mechanics. First they allow one to compute the dynamical susceptibilities, which describe the response of the system to an external time dependent perturbation: the dynamical susceptibilities are, within a multiplicative constant, the time derivatives of Kubo functions. A second crucial property is that transport coefficients can be expressed in terms of time integrals of Kubo functions. As we limit ourselves to small deviations from equilibrium, our theory is restricted to a linear approximation and is known as linear response theory . The classical version of linear reponse is somewhat simpler than the quantum one, and will be described first in Section 9.1. We shall turn to the quantum theory in Section 9.2, where one of our main results will be the proof of the fluctuationdissipation theorem.
This article traces the development of fluctuation theory and its deep connection to irreversibility, from equilibrium to near-equilibrium, and finally to far-from-equilibrium systems. Classical fluctuation theorems, which capture the statistical behaviour of thermodynamic systems far from equilibrium, are now well established. Their quantum counterparts, however, remain an active area of research. In this review, we highlight recent advances by linking quantum fluctuation theorems with linear response theory, offering new insights into the nature of quantum fluctuations and irreversibility in the near-equilibrium regime. Particular emphasis is placed on dissipated work in quantum systems as a pathway to observing non-classical effects in quantum thermodynamics. Understanding quantum fluctuations is not only essential for clarifying the foundations of irreversibility but also crucial for the development of novel quantum technologies, including quantum computers, sensors, and metrological devices.
Abstract This chapter presents a universal definition of linear response, which at first is studied for the example of the damped oscillator. From the quantal time evolution operator lowest order transition rates are deduced, together with microscopic response functions. Their fundamental properties are studied, in particular, the meaning of their reactive and dissipative parts for energy transfer. Correlation functions are introduced and related to response functions by way of the fluctuation dissipation theorem. For a random matrix model, the latter is shown to also hold true for microcanonical ensembles. Connections to thermal Green functions are established and an extension of response theory to unstable modes is discussed. With the help of the Mori product, relations among the static response, the adiabatic and the isothermal susceptibilities are given. Time dependent irreversible processes are studied by introducing relaxation functions and by following the variation of the density operator and of entropy. Onsager relations are presented and Kubo's expressions for transport coefficients are given.
We study the dynamics of a locally conserved energy in ergodic, local many-body quantum systems on a lattice with no additional symmetry. The resulting dynamics is well approximated by a coarse grained, classical linear functional diffusion equation for the probability of all spatial configurations of energy. This is equivalent to nonlinear stochastic hydrodynamics, describing the diffusion of energy in physical spacetime. We find the absence of nonhydrodynamic slow degrees of freedom, a nonlinear fluctuation-dissipation theorem, and the emergence of a (weakly interacting) kinetic theory for hydrodynamic modes near thermal equilibrium. The observable part of the microscopic entropy obeys the local second law of thermodynamics, and quantitatively agrees with the phenomenological predictions of hydrodynamics. Our approach naturally generalizes to ergodic systems with additional symmetries, may lead to numerical algorithms to calculate diffusion constants for lattice models, and implies sufficiency conditions for a rigorous derivation of hydrodynamics in quantum systems.