Long-range excitations in time-dependent density functional theory

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 static correlation created by the step in the exact Kohn-Sham ground-state potential between the two fragments. An approximate non-empirical kernel is derived for excited molecular dissociation curves at large separation. Our result is also relevant for the usual local and semi-local approximations 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.

7 pages, 2 figures

References in corpus (5)

• Time-dependent density functional theory: Past, present, and future
• Describing static correlation in bond dissociation by Kohn-Sham density functional theory
• Excitations in time-dependent density-functional theory
• Undoing static correlation: Long-range charge transfer in time-dependent density functional theory
• Rydberg transition frequencies from the Local Density Approximation

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• Investigating interaction-induced chaos using time-dependent density functional theory
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