Undoing static correlation: Long-range charge transfer in time-dependent density-functional theory

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Abstract

Long-range charge-transfer excited states are notoriously badly underestimated in time-dependent density-functional theory (TDDFT). We discuss how exact TDDFT captures charge transfer between open-shell species: in particular, the role of the step in the ground-state potential, and the severe frequency dependence of the exchange-correlation kernel. An expression for the latter is derived, that becomes exact in the limit that the charge-transfer excitations are well separated from other excitations. The exchange-correlation kernel has the task of undoing the static correlation in the ground state introduced by the step, in order to accurately recover the physical charge-transfer states.

Original languageEnglish (US)
Article number234104
JournalJournal of Chemical Physics
Volume122
Issue number23
DOIs
StatePublished - Jun 15 2005
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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