Many properties of chemical or materials systems are characterized by how they respond to external perturbations. When the external perturbation is sufficiently small that only the leading-order perturbation is important, this is known as the linear response regime. It is in some sense analogous to the linear stability analysis of a dynamical system or that in fluid mechanics. This chapter will give an in-depth discussion of the linear response theory for both static and dynamic perturbations and their applications. The analysis will be from the perspective of the perturbation theory of Green's functions. Towards the end of the chapter, the perturbation theory of a many-body quantum system and its connection to DFT will also be briefly addressed.
Many properties of chemical or materials systems are characterized by how they respond to external perturbations. When the external perturbation is sufficiently small that only the leading-order perturbation is important, this is known as the linear response regime. It is in some sense analogous to the linear stability analysis of a dynamical system or that in fluid mechanics. This chapter will give an in-depth discussion of the linear response theory for both static and dynamic perturbations and their applications. The analysis will be from the perspective of the perturbation theory of Green's functions. Towards the end of the chapter, the perturbation theory of a many-body quantum system and its connection to DFT will also be briefly addressed.
Introduction There are countless situations in physics when one is interested in calculating the response of a system to a small time-dependent perturbation acting on it. With some luck the response can be expanded in a power series of the strength of the perturbation, so that, to first order, it is a linear function of the latter. To compute this function is the objective of the linear response theory (LRT). Linear response theory has many important applications to the study of electronic matter. Virtually all interactions of electrons with experimental probes (electromagnetic fields, beams of particles) can be regarded as small perturbations to the system: if they were not, one would not be probing the system, but the system modified by the probe. Consequently, the results of these experiments can be expressed in terms of linear response functions, which are properties of the unperturbed system. In particular it will turn out that the analytic structure of these functions is entirely determined by the eigenvalues and eigenfunctions of the unperturbed system. Conversely, a measure of the linear response as a function of the frequency of the perturbation enables us to determine the excitation energies of the system. Beside being a cornerstone for the theory of single-particle properties to be developed in Chapter 8, the linear response functions also provide invaluable information in their own right. For example, as we will discuss in Chapter 5, the extent to which an external electrostatic potential is reduced by screening is controlled by the dynamical dielectric function which, in turn, is determined by the density–density response function.
There exists a regime of overlap between the equilibrium and non-equilibrium behavior of a system, the non-equilibrium behavior of weakly perturbed states. When a system is perturbed ever so slightly, its response will be linear in the perturbation, say the current of the conduction electrons in a metal will be proportional to the strength of the applied electric field. This regime is called the linear response regime, and though the system is in a non-equilibrium state all its characteristics can be inferred from the properties of its equilibrium state. In the next chapter we shall go beyond the linear regime by showing how to obtain quantum kinetic equations. The kinetic-equation approach to transport is a general method, and allows in principle nonlinear effects to be considered. However, in many practical situations one is interested only in the linear response of a system to an external force. The linear response limit is a tremendous simplification in comparison with general non-equilibrium conditions, and is the subject matter of this chapter. In particular the linear response of the density and current of an electron gas are discussed. The symmetry properties of response functions, and the fluctuation–dissipation theorem are established. Lastly we demonstrate how correlation functions can be measured in scattering experiments, as illustrated by considering neutron scattering from matter. Needless to say, in measurements of (say) the current in a macroscopic body, far less information in the current correlation function is probed. Linear response In this section we consider the response of an arbitrary property of a system to a general perturbation.
Equilibrium statistical mechanics is a first principle theory whose fundamental statements are general and independent of the details associated with individual systems. No such general theory exists for nonequilibrium systems and for this reason we often have to resort to ad hoc descriptions, often of phenomenological nature, as demonstrated by several examples in Chapters 7 and 8. Equilibrium statistical mechanics can however be extended to describe small deviations from equilibrium in a way that preserves its general nature. The result is Linear Response Theory, a statistical mechanical perturbative expansion about equilibrium. In a standard application we start with a system in thermal equilibrium and attempt to quantify its response to an applied (static- or time-dependent) perturbation. The latter is assumed small, allowing us to keep only linear terms in a perturbative expansion. This leads to a linear relationship between this perturbation and the resulting response. Let us make these statements more quantitative. Consider a system characterized by the Hamiltonian Ĥ0.
In this primer to the many-body theory of condensed-matter systems, the authors introduce the subject to the non-specialist in a broad, concise, and up-to-date manner. A wide range of topics are covered including the second quantization of operators, coherent states, quantum-mechanical Green's functions, linear response theory, and Feynman diagrammatic perturbation theory. Material is also incorporated from quantum optics, low-dimensional systems such as graphene, and localized excitations in systems with boundaries as in nanoscale materials. Over 100 problems are included at the end of chapters, which are used both to consolidate concepts and to introduce new material. This book is suitable as a teaching tool for graduate courses and is ideal for non-specialist students and researchers working in physics, materials science, chemistry, or applied mathematics who want to use the tools of many-body theory.
In this primer to the many-body theory of condensed-matter systems, the authors introduce the subject to the non-specialist in a broad, concise, and up-to-date manner. A wide range of topics are covered including the second quantization of operators, coherent states, quantum-mechanical Green's functions, linear response theory, and Feynman diagrammatic perturbation theory. Material is also incorporated from quantum optics, low-dimensional systems such as graphene, and localized excitations in systems with boundaries as in nanoscale materials. Over 100 problems are included at the end of chapters, which are used both to consolidate concepts and to introduce new material. This book is suitable as a teaching tool for graduate courses and is ideal for non-specialist students and researchers working in physics, materials science, chemistry, or applied mathematics who want to use the tools of many-body theory.
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.