Long-range excitations in time-dependent density functional theory

Neepa T. Maitra, David G. Tempel

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53 Scopus citations

Abstract

Adiabatic time-dependent density functional theory fails for excitations of a heteroatomic molecule composed of two open-shell fragments at large separation. Strong frequency dependence of the exchange-correlation kernel is necessary for both local and charge-transfer excitations. The root of this is the static correlation created by the step in the exact Kohn-Sham ground-state potential between the two fragments. An approximate nonempirical kernel is derived for excited molecular dissociation curves at large separation. Our result is also relevant when the usual local and semilocal approximations are used for the ground-state potential, as static correlation there arises from the coalescence of the highest occupied and lowest unoccupied orbital energies as the molecule dissociates.

Original languageEnglish (US)
Article number184111
JournalJournal of Chemical Physics
Volume125
Issue number18
DOIs
StatePublished - 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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