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Long-range excitations in time-dependent density functional theory.

Neepa T Maitra1, David G Tempel

  • 1Department of Physics and Astronomy, Hunter College of the City University of New York, New York, New York 10021, USA. mmaitra@hunter.cuny.edu

The Journal of Chemical Physics
|November 23, 2006
PubMed
Summary
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Adiabatic time-dependent density functional theory struggles with excited heteroatomic molecules. A frequency-dependent kernel is crucial for accurate calculations, especially for charge-transfer excitations.

Area of Science:

  • Computational chemistry
  • Quantum mechanics
  • Electronic structure theory

Background:

  • Adiabatic time-dependent density functional theory (TDDFT) is a common method for calculating molecular excitations.
  • Standard approximations in TDDFT often fail for systems with strong static correlation, such as heteroatomic molecules at large separations.

Purpose of the Study:

  • To investigate the limitations of adiabatic TDDFT for excited states of heteroatomic molecules composed of open-shell fragments.
  • To identify the necessary components for accurate theoretical descriptions of such systems.

Main Methods:

  • Analysis of the failure of adiabatic TDDFT for specific molecular systems.
  • Investigation of the role of static correlation in the Kohn-Sham ground-state potential.
  • Derivation of an approximate nonempirical kernel for excited molecular dissociation.

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Main Results:

  • Adiabatic TDDFT fails for excitations of heteroatomic molecules with two open-shell fragments at large distances.
  • Strong frequency dependence in the exchange-correlation kernel is essential for describing both local and charge-transfer excitations.
  • Static correlation, arising from the Kohn-Sham potential step, is identified as the root cause of the failure.

Conclusions:

  • A frequency-dependent exchange-correlation kernel is necessary for accurate excited-state calculations in these systems.
  • The derived approximate kernel can be used for excited molecular dissociation curves at large separations.
  • The findings are relevant even for standard ground-state potential approximations where static correlation emerges during dissociation.