Theoretical Calculations of Kinetic Isotope Effects for a Series of Aziridines
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)
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.
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
IdentifiersURN: urn:nbn:se:uu:diva-91651ISBN: 978-1-4020-2583-9ISBN: 978-90-481-6687-9OAI: oai:DiVA.org:uu-91651DiVA: diva2:164452