Exact-exchange time-dependent density-functional theory for static and dynamic polarizabilities

So Hirata, Stanislav Ivanov, Rodney J. Bartlett, Ireneusz Grabowski

Research output: Contribution to journalArticle

Abstract

Time-dependent density-functional theory (TDDFT) employing the exact-exchange functional has been formulated on the basis of the optimized-effective-potential (OEP) method of Talman and Shadwick for second-order molecular properties and implemented into a Gaussian-basis-set, trial-vector algorithm. The only approximation involved, apart from the lack of correlation effects and the use of Gaussian-type basis functions, was the consistent use of the adiabatic approximation in the exchange kernel and in the linear response function. The static and dynamic polarizabilities and their anisotropy predicted by the TDDFT with exact exchange (TDOEP) agree accurately with the corresponding values from time-dependent Hartree-Fock theory, the exact-exchange counterpart in the wave function theory. The TDOEP is free from the nonphysical asymptotic decay of the exchange potential of most conventional density functionals or from any other mani-festations of the incomplete cancellation of the self-interaction energy. The systematic overestimation of the absolute values and dispersion of polarizabilities that plagues most conventional TDDFT cannot be seen in the TDOEP.

Original languageEnglish (US)
Article number032507
JournalPhysical Review A - Atomic, Molecular, and Optical Physics
Volume71
Issue number3
DOIs
StatePublished - Mar 1 2005
Externally publishedYes

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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