Local exchange potentials for electronic structure calculations

Nonlinear elliptic equations (35J60) Nonlinear eigenvalue problems and nonlinear spectral theory for PDEs (35P30) Applications of operator theory in the physical sciences (47N50) Closed and approximate solutions to the Schrödinger, Dirac, Klein-Gordon and other equations of quantum mechanics (81Q05)

Abstract: The Hartree-Fock exchange operator is an integral operator arising in the Hartree-Fock method and replaced by a multiplicative operator (a local potential) in Kohn-Sham density functional theory. This article presents a detailed analysis of the mathematical properties of various local approximations to the nonlocal Hartree-Fock exchange operator, including the Slater potential, the optimized effective potential (OEP), the Krieger-Li-Iafrate (KLI) and common energy-denominator approximations (CEDA) to the OEP, and the effective local potential (ELP). In particular, we show that the Slater, KLI, CEDA potentials and the ELP can all be defined as solutions to certain variational problems. We also provide a rigorous derivation of the integral OEP equation and establish the existence of a solution to a system of coupled nonlinear partial differential equations defining the Slater approximation to the Hartree-Fock equations.

Review text

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.

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