A Theoretical Examination of the Potential Energy Surface of α-peroxyacetaldehyde in the Gas Phase and in Dichloromethane
Bayci, Andrew W. L.
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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.