Local exchange potentials for electronic structure calculations (Q1020632)

The Hartree-Fock exchange operator is the most computationally demanding term in the Hartree-Fock equations arising in the Hartree-Fock model for the electronic state of a system of finite electrons. Back in the early days of quantum chemistry, \textit{J.\,C.\thinspace Slater} [Phys.\ Rev., II.\,Ser.\ 81, 385--390 (1951; Zbl 0042.23202)] proposed to approximate the Hartree-Fock exchange operator by a more tractable local potential, i.e., by a multiplicative operator. Motivated by Slater's work, several variational methods for obtaining local potentials were introduced, including the optimized effective potential (OEP), the Krieger-Li-Iafrate (KLI) approximation and the common-energy denominator approximation (CEDA) to the OEP, and the effective local potential (ELP). This paper presents a detailed analysis of the mathematical properties of these various local approximations to the nonlocal Hartree-Fock exchange operator. In particular, the authors show that the Slater, KLI, CEDA and ELP potentials all can be defined as solutions of certain variational problems and provide a rigorous derivation of the OEP integral equation. They also establish an existence result for a coupled system of nonlinear partial differential equations introduced by Slater to approximate the Hartree-Fock equations.