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On the convergence of SCF algorithms for the Hartree-Fock equations. (English) Zbl 1090.65548
Summary: The present work is a mathematical analysis of two algorithms, namely the Roothaan and the level-shifting algorithms, commonly used in practice to solve the Hartree-Fock equations. The level-shifting algorithm is proved to be well-posed and to converge provided the shift parameter is large enough. On the contrary, cases when the Roothaan algorithm is not well defined or fails in converging are exhibited. These mathematical results are confronted to numerical experiments performed by chemists.

MSC:
65N35 Spectral, collocation and related methods for boundary value problems involving PDEs
35P30 Nonlinear eigenvalue problems and nonlinear spectral theory for PDEs
81-08 Computational methods for problems pertaining to quantum theory
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