Density-Functional Methods for Excited States

Katarzyna Pernal, Klaas J. H. Giesbertz

Recent advances in reduced density matrix functional theory (RDMFT) and linear response time-dependent reduced density matrix functional theory (TD-RDMFT) are reviewed. In particular, we present various approaches to develop approximate density matrix functionals which have been employed in RDMFT. We discuss the properties and performance of most available density matrix functionals. Progress in the development of functionals has been paralleled by formulation of novel RDMFT-based methods for predicting properties of molecular systems and solids. We give an overview of these methods. The time-dependent extension, TD-RDMFT, is a relatively new theory still awaiting practical and generally useful functionals which would work within the adiabatic approximation. In this chapter we concentrate on the formulation of TD-RDMFT response equations and various adiabatic approximations. None of the adiabatic approximations is fully satisfactory, so we also discuss a phase-dependent extension to TD-RDMFT employing the concept of phase-including-natural-spinorbitals (PINOs). We focus on applications of the linear response formulations to two-electron systems, for which the (almost) exact functional is known.