The Linear Response Function Theory

Michael G Cottam, Zahra Haghshenasfard

Mizuhiko Saeki

Carsten A. Ullrich

This chapter discusses the linear-response framework of time-dependent density-functional theory (TDDFT). It begins with a thorough and self-contained exposition of general linear-response theory for many-body systems. The time-dependent as well as the frequency-dependent response are discussed. Several exact representations and properties of the density-density response function are reviewed, such as the Lehmann representation and fluctuation-dissipation theorem, and the Kramers-Kronig relations. It is shown how several important spectroscopic observables are obtained from linear-response theory. Then, the TDDFT formulation of linear-response theory is derived. The key quantity in this formalism is the so-called exchange-correlation kernel. The remainder of the chapter demonstrates how this linear-response formalism can be used to calculate excitation energies in principle exactly with TDDFT. The Casida equation is derived, as well as several approximate schemes. A comparison is made with time-dependent Hartree-Fock theory.

Gabriele F. Giuliani, Giovanni Vignale

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.

Fabrizio Tafuri, C. A. Perroni, G. De Filippis