Relativistic Density Functional Theory Foundations and Basic Formalism

RELATIVISTIC DENSITY FUNCTIONAL THEORY FOUNDATIONS AND BASIC FORMALISM 

An overview of relativistic density functional theory (RDFT) is presented with special emphasis on its field theoretical foundations and the construction of relativistic density functionals. A summary of quantum electrodynamics (QED) for bound states provides the background for the discussion of the relativistic generalization of the Hohenberg-Kohn theorem and the effective single-particle equations of RDFT. In particular, the renormalization procedure of bound state QED is reviewed in some detail. Knowledge of this renormalization scheme is pertinent for a careful derivation of the RDFT concept which necessarily has to reflect all the features of QED, such as transverse and vacuum corrections. This aspect not only shows up in the existence proof of RDFT, but also leads to an extended form of the single-particle equations which includes radiative corrections. The need for renormalization is also evident in the construction of explicit functionals. 

In spite of the impressive progress which has been achieved with conventional ab-initio methods as the Configuration-Interaction or Coupled-Cluster schemes in recent years density functional theory (DFT) still represents the method of choice for the study of complex many-electron systems (for an overview of DFT see [1]). Today DFT covers an enormous variety of fields, ranging from atomic [2,3], cluster [4,5] and surface physics [6,7] to the material sciences [8-10]. and theoretical biophysics [11-13]. Moreover, since the introduction of the generalized gradient approximation DFT has become an accepted method also for standard quantum chemical applications [14,15]. Given this tremendous success of nonrelativistic DFT the question for a relativistic extension (RDFT) arises quite naturally in view of the large number of problems in which relativistic effects play an important role (see e.g. Refs.[16,17]). 

This statement implies that not only the Coulomb interaction is included in Er and Exc but also the (retarded) Breit interaction. It thus points at the fact that a consistent and complete discussion of many-electron systems and consequently of RDFT must start from quantum electrodynamics (QED). RDFT necessruily has to reflect the various features of QED, both on the formal level and in the derivation of explicit functionals. The most important differences to the noiu-elativistic situation arise from the presence of infinite zero point energies and ultraviolet divergencies. In addition, finite vacuum corrections (vacuum polarization, Casimir energy) show up in both fundamental quantities of RDFT, the four current and the total energy. These issues have to be dealt with by a suitable renormalization procedure which ultimately relies on the renormalization of the vacuum Greens functions of QED. The first attempt to take 

The fact that in the RLDA the xc-functional only depends on the density, rather than on the full four current, has stimulated the search for alternative forms of RDFT which allow an explicit treatment of magnetization effects, 

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Engel, E. Keller, S. Dreizler, R. M. Phys. Rev. A 1996, 53, 1367-1374 Engel, E. Relativistic density functional theory foundations and basic formalism. In Relativistic Electronic Structure... 

Engel, E. Relativistic density functional theory Foundations and basic formalism. In Schwerdtfeger, P. (ed.) Relativistic Electronic Structure Theory, Part I, pp. 523-621. Elsevier, Amsterdam (2002)... 

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