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dc.contributor.authorUllrich, Carsten A.eng
dc.contributor.authorBurke, Kieroneng
dc.date.issued2004eng
dc.descriptiondoi:10.1063/1.1756865eng
dc.description.abstractTime-dependent density-functional theory in the adiabatic approximation has been very successful for calculating excitation energies in molecular systems. This paper studies nonadiabatic effects for excitation energies, using the current-density functional of Vignale and Kohn [Phys. Rev. Lett. 77, 2037 (1996)]. We derive a general analytic expression for nonadiabatic corrections to excitation energies of finite systems and calculate singlet s→s and s→p excitations of closed-shell atoms. The approach works well for s→s excitations, giving a small improvement over the adiabatic local-density approximation, but tends to overcorrect s→p excitations. We find that the observed problems with the nonadiabatic correction have two main sources: (1) the currents associated with the s→p excitations are highly nonuniform and, in particular, change direction between atomic shells, (2) the so-called exchange-correlation kernels of the homogeneous electron gas, fxcL and fxcT, are incompletely known, in particular in the high-density atomic core regions.eng
dc.description.sponsorshipC.A.U. acknowledges support by the donors of the Petroleum Research Fund, administered by the ACS, and by the University of Missouri Research Board. K.B. was supported by DOE under Grant No. DE-FG02-01ER45928.eng
dc.identifier.citationJ. Chem. Phys. 121, 28 (2004)eng
dc.identifier.issn0021-9606eng
dc.identifier.urihttp://hdl.handle.net/10355/7615eng
dc.languageEnglisheng
dc.publisherAmerican Institute of Physicseng
dc.relation.ispartofcollectionUniversity of Missouri--Columbia. College of Arts and Sciences. Department of Physics and Astronomy. Physics and Astronomy publicationseng
dc.subjectelectron correlation calculations for atoms and ionseng
dc.subjectexcited stateseng
dc.subject.lcshDensity functionalseng
dc.subject.lcshEnergy levels (Quantum mechanics)eng
dc.subject.lcshElectron configurationeng
dc.titleExcitation energies from time-dependent density-functional theory beyond the adiabatic approximationeng
dc.typeArticleeng


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