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Theoretical Calculations of Kinetic Isotope Effects for a Series of Aziridines
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
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2004 (English)In: Fundamental World of Quantum Chemistry: A Tribute to the Memory of Per-Olov Löwdin, Volume 3 / [ed] Brändas, Erkki J. and Kryachko, Eugene S., Dordrecht: Kluwer Academic Publishers , 2004Chapter in book (Refereed)
Abstract [en]

The nitrogen inversion in aziridine and som parent substituted aziridines is investigated using various computational methods. The stationary points on each potential energy surface are optimized using the B3LYP functional of density functional theory (DFT) in conjuction with the popular 6-31G(d) basis set. Rate constants and thereby kinetic isotope effects (KIEs) are computed at different temperatures using transiton state theory (TST) and various techniques of variational transition state theory (VTST). Moreover, corrections are made for tunneling and non-classical reflection, using three semiclassic correction methods: the Wigner tunneling correction as well as the zero-curvature and the samll-curvature corrections. The performance of the various methods to compute KIEs are compared and the effects of tunneling are discussed.

Place, publisher, year, edition, pages
Dordrecht: Kluwer Academic Publishers , 2004.
Keyword [en]
Aziridnie, nitrogen inversion, kinetic isotope, effect, density functional theory calculations, variational transition state theory, Wigner-tunneling correction, zero-curvature tunneling correction, small-curvature tunneling correction
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-91651ISBN: 978-1-4020-2583-9 (print)ISBN: 978-90-481-6687-9 (print)OAI: oai:DiVA.org:uu-91651DiVA: diva2:164452
Available from: 2004-04-15 Created: 2004-04-15 Last updated: 2011-04-09Bibliographically approved
In thesis
1. Quantum Chemical Calculations on ESR, Core Excitations, and Isotope Effects in Molecular Systems
Open this publication in new window or tab >>Quantum Chemical Calculations on ESR, Core Excitations, and Isotope Effects in Molecular Systems
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, quantum chemical calculations are undertaken mostly in order to interpret experimental results, but also to learn about computational techniques, their performance and their limitations. In paper I, the ionization-cleavage process of alkenes is investigated and two pathways are followed, one of initial cleavage and subsequent ionization and on the opposite, the other one of initial ionization and subsequent cleavage. The calculations reveal that ionization is best described by a vertical process, which is much faster than the relaxation of the molecule to its ionized structural minimum. Further, in paper II, the core hole excited state of ammonia is investigated and found to dissociate in an ultra-fast manner nicely explained by the calculated potential energy surface showing a very low barrier for dissociation. In paper III, the static and dynamic structures of two halogenated dimethyl ether radical cations are studied in ESR experiments, and it is found that, while the chlorinated molecule remains unaffected, the fluorinated molecule undergoes a dissociation or association reaction before the measurement takes place, the resulting fragments are searched for but not identified decisively. In paper IV, the stability of Jahn-Teller distorted selectively deuteriated benzene radical cation isotopomers is investigated by ESR experiments and density functional theory calculations. The temperature dependence, between 4.2 K and 77 K, of the ESR spectra is explained. Finally, in paper V, the hydrogen inversion in aziridine and methyl and dimethyl substituted aziridines is investigated. The rate constants and kinetic isotope effects are calculated using various techniques of transition state theory and tunneling correction methods.

Publisher
42 p.
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 966
Keyword
Quantum chemistry, Kvantkemi
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:uu:diva-4226 (URN)91-554-5943-9 (ISBN)
Public defence
2004-05-07, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15
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Supervisors
Available from: 2004-04-15 Created: 2004-04-15Bibliographically approved

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Salhi-Benachenhou, NessimaBergson, GöranLunell, Sten

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