On Convergence Difficulties in the Iterative Hartree—Fock Procedure
- 1 September 1971
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 55 (5), 2408-2413
- https://doi.org/10.1063/1.1676424
Abstract
Different procedures for solving the nonlinear Hartree—Fock problem are analyzed. The classical iterative procedure involving recalculation of the one‐electron density matrix in each step does not depend only on local properties of the one‐electron density matrix in the previous step. Convergence difficulties arising from this fact are exhibited and analyzed for a diatomic molecule. There can result oscillation of atomic charges for larger internuclear distances. The resulting bond‐order matrix does not correspond to any extremum of the expectation value of the Hamiltonian. Illustrative numerical examples are presented. Calculations for the PPP model of polyatomic chains show that the same effect can occur even for configurations slightly different from equilibrium ones.This publication has 16 references indexed in Scilit:
- Optimization of SCF LCAO wave functionsMolecular Physics, 1970
- The determination of SCF LCAO solutions for open shell configurationsTheoretical Chemistry Accounts, 1968
- Application of Nonlinear Transformations to the Evaluation of Multicenter IntegralsThe Journal of Chemical Physics, 1967
- Multi-Configuration Self-Consistent-Field TheoryProgress of Theoretical Physics Supplement, 1967
- Computer Programs for Electronic Wave-Function CalculationsReviews of Modern Physics, 1963
- Some Recent Advances in Density Matrix TheoryReviews of Modern Physics, 1960
- The density matrix in self-consistent field theory I. Iterative construction of the density matrixProceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, 1956
- The bond orders of alternant hydrocarbon moleculesProceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, 1955
- Wave Functions and Energy Levels foras Found by the Slater Approximation to the Hartree-Fock EquationsPhysical Review B, 1952
- New Developments in Molecular Orbital TheoryReviews of Modern Physics, 1951