Natural orbital analysis of ultrafast multielectron dynamics of molecules

Hirohiko Kono, Takayuki Oyamada, Tsuyoshi Kato, Shiro Koseki

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

The ionization dynamics of molecules in intense laser fields is investigated by using a time-dependent multiconfiguration theory for propagating the many-electron wave function in a grid space. We use the natural orbitals obtained from the many-electron wave function, i.e., the molecular orbitals obtained by diagonalizing the one-particle electron density matrix, to analyze the ionization process.We eliminate the ionizing portions of orbitals reaching the grid boundaries set far away from the nuclei; the occupation numbers of natural orbitals decrease due to ionization. The ionization probabilities of individual natural orbitals can be obtained from the accumulated reductions in occupation numbers. We also propose a new definition of molecular orbital energy in order to investigate the energetics of natural orbitals. It is shown that when energies are assigned to natural orbitals {φj(t)} as chemical potentials {εj(t)}, one can quantify a correction to the total electronic energy that represents electron correlation; that is, time-dependent correlation energy is introduced. Our attempt is illustrated by numerical results on the time-dependence of the spatial density and chemical potential 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 Δεj(t) in the chemical potential for φj(t) and found that energy accepting orbitals of Δεj(t) > ζj(t) exhibit high ionization efficiency.

Original languageEnglish
Title of host publicationMultiphoton Processes and Attosecond Physics - Proceedings of the 12th Int. Conference on Multiphoton Processes, ICOMP 2011 and the 3rd International Conference on Attosecond Physics, ATTO 2011
PublisherSpringer Science and Business Media, LLC
Pages289-297
Number of pages9
ISBN (Print)9783642289477
DOIs
Publication statusPublished - 2012
Event12th International Conference on Multiphoton Processes, ICOMP 2011 and the 3rd International Conference on Attosecond Physics, ATTO 2011 - Sapporo, Hokkaido, Japan
Duration: 2011 Jul 32011 Jul 8

Publication series

NameSpringer Proceedings in Physics
Volume125
ISSN (Print)0930-8989
ISSN (Electronic)1867-4941

Other

Other12th International Conference on Multiphoton Processes, ICOMP 2011 and the 3rd International Conference on Attosecond Physics, ATTO 2011
CountryJapan
CitySapporo, Hokkaido
Period11/7/311/7/8

ASJC Scopus subject areas

  • Physics and Astronomy(all)

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