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

Journal Article · Tue Mar 01 04:00:00 EST 2005 · Physical Review. A

DOI:https://doi.org/10.1103/PhysRevA.71.032507· OSTI ID:20650395

Hirata, So; Ivanov, Stanislav; Bartlett, Rodney J; Grabowski, Ireneusz ^[1]

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1. Quantum Theory Project, Department of Chemistry, University of Florida, Gainesville, Florida 32611-8435 (United States)

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 manifestations 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.

• OSTI ID: 20650395
• Journal Information: Physical Review. A, Journal Name: Physical Review. A Journal Issue: 3 Vol. 71; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ADIABATIC APPROXIMATION
ALGORITHMS
ANISOTROPY
CORRELATIONS
DECAY
DENSITY FUNCTIONAL METHOD
HARTREE-FOCK METHOD
POLARIZABILITY
POTENTIALS
RESPONSE FUNCTIONS
TIME DEPENDENCE
VECTORS
WAVE FUNCTIONS