Dissertation/Thesis Abstract

Fully Fledged Frozen Dihedral Approach to Compute Tunneling Ready State Structures and Gating Coordinate
by Sakhaee, Nader, M.S., Southern Illinois University at Edwardsville, 2018, 61; 10843953
Abstract (Summary)

Hydride tunneling is among the most debated mechanism in physical organic chemistry and it has been gradually accepted by most specialists in the field as a potent tool to back up unusual kinetic isotope effects (KIE) for both primary 1 and Secondary 2 KIE’s. Those who are in favor of the tunneling mechanism, mainly claim the small size of the hydrogen and its diffuse wave packet to be responsible for the effective through the barrier tunneling. Yet how exactly this tunneling mechanism happens and what factors promote such a mechanism has opened up a brand new field which has attracted not only organic biochemists and physical organic scientists but has also been alluring to chemical physicists as well. The latter groups of scientists are trying to use detailed quantum mechanical models, strong enough to explain all of the observed KIE’s within just one firm and universally accepted frame. Such models may include the Marcus-like model and transition state theory extension (TST extension) model, both of which explain the complex reaction coordinate for hydride transfer reactions. In this study we try to compute tunneling ready state (TRS) structures, and the so-called gating coordinate in order to obtain a better understanding of reaction coordinate in hydride transfer reactions.

Indexing (document details)
Advisor: Ackad, Edward, Lu, Yun
Commitee: Glassman, Jack, O' Brien, Leah
School: Southern Illinois University at Edwardsville
Department: Integrative Studies
School Location: United States -- Illinois
Source: MAI 58/02M(E), Masters Abstracts International
Subjects: Chemistry, Physics
Keywords: Born-Oppenheimer, Donor acceptor distance, Extension to transition state theory, Frank-Condon, Kinetic isotope effect, Tunneling ready state
Publication Number: 10843953
ISBN: 978-0-438-39394-3
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