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.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
