A Theoretical Examination of the Potential Energy Surface of α-peroxyacetaldehyde in the Gas Phase and in Dichloromethane
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Authors
Bayci, Andrew W. L.
Issue Date
2006
Type
Thesis
Language
Keywords
Alternative Title
Abstract
Autooxidation (AO) refers to the oxidation of organic compounds by
molecular oxygen.AO reactions of a-methylene ketones generally involve reactive
intermediate species which results in a varied product composition. In this study, a
computational approach is used to help explain the product diversity associated with
these types of reactions. Gaussian program was used to perform density functional
theory (DFT) computations of the potential energy surface of a-peroxyacetaldehyde
in the gas phase using the b31yp/6-31 l+g(d,p)//b31yp/6-31-i-g(d) functional and basis
sets. To model this surface in dichloromethane, the integral equation formalism of the
polarizable continuum model (IEFPCM) was used in conjunction with the Universal
force field (UFF) atomic radii set to compute solvated geometries of minima and
transition states in a solvent accessible cavity with the b31yp/6-31+g(d) method.
Single-point energies of solvated geometries were calculatedwith the isodensity
polarizable continuum model (IPCM) using the b31yp/6-31 l+g(d,p) method. This
study was successful in determining the energies and geometries of various minima
and transition stateson the gas phase and solvated potential energysurfaces of aperoxyacetaldehydeand
will be useful in showing how and why AO reactions of a
particular starting material in a certain reaction environment produce a specific
product mixture.
Description
vii, 79 p.
Citation
Publisher
Kalamazoo College
License
U.S. copyright laws protect this material. Commercial use or distribution of this material is not permitted without prior written permission of the copyright holder. All rights reserved.