Convergence of SCF Sequences for the Hartree-Fock Equation

J. Math. Sci. Univ. Tokyo
Vol. 30 (2023), No. 3, Page 241–285.

Ashida, Sohei
Convergence of SCF Sequences for the Hartree-Fock Equation
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The Hartree-Fock equation is a fundamental equation in many-electron problems. It is of practical importance in quantum chemistry to find solutions to the Hartree-Fock equation. The self-consistent field (SCF) method is a standard numerical calculation method to solve the Hartree-Fock equation. In this paper we prove that the sequence of the functions obtained in the SCF procedure is composed of a sequence of pairs of functions that converges after multiplication by appropriate unitary matrices, which strongly ensures the validity of the SCF method. A sufficient condition for the limit to be a solution to the Hartree-Fock equation after multiplication by a unitary matrix is given, and the convergence of the corresponding density operators is also proved. The method is based mainly on the proof of approach of the sequence to a critical set of a functional, compactness of the critical set, and the proof of Lojasiewicz inequality for another functional near critical points.

Keywords: Hartree-Fock equation, SCF method, convergence analysis, Lojasiewicz inequality.

Mathematics Subject Classification (2020): Primary 81-08; Secondary 65K10.
Received: 2022-05-24