Quantum mechanical tunneling plays a role in many reactions involving hydrogen transfer, yet it is often difficult to determine how much tunneling contributes to the overall rate because it usually competes with the quasi-classical rate of reaction.  If tunneling is significant however, it will affect observable parameters such as the kinetic isotope effect (KIE), Arrhenius parameters (A and Ea), and Swain-Schaad exponents (SSE).  This poster will explore multidimensional tunneling effects on the rates of nitrogen inversion.  First, the rates and H/D KIE will be calculated using POLYRATE and GAUSSIAN03 with mPW1K/6-31+G(p,d) methodology for nitrogen inversion in aziridine since its rates and H/D KIE have been measured experimentally and calculated with various tunneling models.  Then we will present results on the effect of tunneling on the double nitrogen inversion in diaziridine and bis-aziridine to see how tunneling affects the KIE for both the concert and stepwise mechanisms of double nitrogen inversion.

Multidimensional tunneling effects on nitrogen inversion in aziridine, diaziridine, and bis-aziridine

243rd National Meeting (2012)

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