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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:
 10895639(20010906)105:35<8236:SRIABE>2.0.ZU;2C
 Fonte:
 ISI
 Lingua:
 ENG
 Soggetto:
 POTENTIALENERGY SURFACE; ABINITIO; HARTREEFOCK; 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. 82368240
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 (2,3X,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 HartreeFock 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 twostate 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.
ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 04/12/20 alle ore 16:29:31