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Titolo:
Symmetry, radical ions, and butadienes: Exploring the limits of density functional theory
Autore:
Oxgaard, J; Wiest, O;
Indirizzi:
Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA Univ Notre Dame Notre Dame IN USA 46556 Biochem, Notre Dame, IN 46556 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 35, volume: 105, anno: 2001,
pagine: 8236 - 8240
SICI:
1089-5639(20010906)105:35<8236:SRIABE>2.0.ZU;2-C
Fonte:
ISI
Lingua:
ENG
Soggetto:
POTENTIAL-ENERGY SURFACE; AB-INITIO; HARTREE-FOCK; CATION; DYNAMICS; REARRANGEMENTS; DISSOCIATION; FAILURE; POINT; STATE;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
37
Recensione:
Indirizzi per estratti:
Indirizzo: Wiest, O Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA Univ Notre Dame Notre Dame IN USA 46556 Notre Dame, IN 46556 USA
Citazione:
J. Oxgaard e O. Wiest, "Symmetry, radical ions, and butadienes: Exploring the limits of density functional theory", J PHYS CH A, 105(35), 2001, pp. 8236-8240

Abstract

Pure and hybrid density functional theory (DFT) methods are evaluated regarding their ability to correctly describe asymmetric transition structures for symmetric butadiene radical cations. The study covers unsubstituted butadiene radical cation as well as (2,3-X,X)-disubstituted butadiene radical cations, where X is -CH3, -OH, -F, or -SiH3. The DFT methods either converge toward an erroneous symmetric solution or describe the asymmetric transition structure qualitatively correctly. Whether or not the asymmetric transition structure is found depends on the amount of Hartree-Fock density exchange included in the method, as well as on the electronic characteristics ofthe substituents, as described by their ol values. The disparate behaviorsencountered are rationalized by a two-state model. It is also shown that molecular symmetry does not automatically induce, errors, as reported by earlier studies. Instead, electronic symmetry is introduced as a factor to observe when organic radical cations are studied computationally.

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Documento generato il 04/12/20 alle ore 16:29:31