Time-dependent multiconfiguration theory for ultrafast electronic dynamics of molecules in an intense laser field: Electron correlation and energy redistribution among natural orbitals

Tsuyoshi Kato, Hirohiko Kono

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

We propose a new definition of molecular orbital energy in order to investigate the energetics of constituent molecular orbitals in the many-electron wave function calculated based on time-dependent multiconfiguration theory. It is shown that when energies are assigned to natural orbitals by a similar manner to that used in the Hartree-Fock theory, we can quantify a correction energy to the total electronic energy that represents electron correlation, and thus we can evaluate the time-dependence of the correlation energy. Our attempt is illustrated by numerical results on the time-dependence of the spatial density of the correlation energy and the orbital energies for a H2 molecule interacting with an intense, near-infrared laser field. We compared the energy ζj(t) supplied by the applied field with the net energy gain Δ over(ε{lunate}, ̄)j (t) for respective natural orbitals φ{symbol}j(t). φ{symbol}j and found that the natural orbitals with Δ over(ε{lunate}, ̄)j (t) > ζj (t) play a key role in the ionization process.

Original languageEnglish
Pages (from-to)46-53
Number of pages8
JournalChemical Physics
Volume366
Issue number1-3
DOIs
Publication statusPublished - 2009 Dec 10

Keywords

  • Electron correlations
  • Intense laser field
  • Multiconfiguration time-dependent Hartree-Fock (MCTDHF)
  • Natural orbitals

ASJC Scopus subject areas

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

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