A theoretical examination of the potential energy surface of α-peroxyacetaldehyde in the gas phase and in dichloromethane

CHED 513

Andrew W. L. Bayci, k03ab02@kzoo.edu1, John Hofferberth, hofferberthj@kenyon.edu2, and Kristin Hofferberth, hofferberthk@kenyon.edu2. (1) Department of Chemistry, Kalamazoo College, 1200 Academy St., Kalamazoo, MI 49006, (2) Department of Chemistry, Kenyon College, Tomsich Hall, Gambier, OH 43022
Autooxidation (AO) reactions of α-methylene ketones generally involve reactive intermediate species and result in a varied product composition. To help explain the product diversity associated with these types of reactions, DFT was used to compute the potential energy surface of α-peroxyacetaldehyde in the gas phase using the b3lyp/6-311+g(d,p)//b3lyp/6-31+g(d) functionals and basis sets. The IEFPCM was used in conjunction with the UFF radii set to compute solvated geometries of minima and transition states in a solvent accessible cavity in dichloromethane with the b3lyp/6-31+g(d) method. Single-point energies of solvated geometries were calculated with the IPCM using the b3lyp/6-311+g(d,p) method. This study was successful in determining the energies and geometries of various minima and transition states on the gas phase and solvated potential energy surfaces of α-peroxyacetaldehyde and will be useful in demonstrating how and why AO reactions involving a certain starting material and reaction environment produce a particular product mixture.