Fock matrix dynamics

Peter Pulay, Géza Fogarasi

Research output: Contribution to journalArticle

66 Citations (Scopus)


An efficient method is suggested for direct ab initio Born-Oppenheimer molecular dynamics. It is based on extrapolating the Fock matrices from previous time steps to provide a start for the SCF procedure. Several polynomial extrapolation schemes are compared; low-degree schemes work best. SCF convergence can be achieved in 2-3, sometimes less than two cycles. We have identified a phenomenon, hysteresis, a violation of the energy conservation and reversibility, due to systematic errors arising from incomplete SCF convergence. It can be eliminated by rescaling the velocities. Examples include water clusters and hydrated halogen ions, running simulations for several picoseconds.

Original languageEnglish
Pages (from-to)272-278
Number of pages7
JournalChemical Physics Letters
Issue number4-6
Publication statusPublished - Mar 11 2004


ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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