DFT study of the explosive tetraacetone tetraperoxide

COMP 180

Jeffrey N Woodford, jeff.woodford@eou.edu1, Gerard S. Harbison, gerry@chem-gharbison.unl.edu2, Paul Goodman3, and Jody G. Redepenning3. (1) Department of Chemistry and Biochemistry, Eastern Oregon University, One University Boulevard, La Grande, OR 97850-2899, (2) Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE, (3) Department of Chemistry, University of Nebraska, Lincoln, NE 68588-0304
Peroxide-based explosives have been implicated in many acts of terrorism around the world. They remain a major cause of concern because of their ease of synthesis and difficulty in detection. In order to improve our understanding of this important class of molecules, theoretical calculations were performed on tetraacetone tetraperoxide (TeATeP) using density functional theory. The results predict the existence of many conformers, but only one, having pseudo-D4 symmetry, should dominate the equilibrium properties of TeATeP. Thermochemical analysis suggests that it is not as thermodynamically stable as other peroxide-based explosives; the ring diameter is too small to accommodate fully trans O-O linkages but too large to permit gauche conformers. For this reason, synthesis of this compound may be more difficult than has previously been assumed. The computed 1H and 13C NMR spectra and harmonic vibrational frequencies show marked differences between TeATeP and the spectral properties of related peroxide-based explosives, which may assist in the detection of TeATeP. Preliminary experimental evidence on the synthesis of TeATeP will also be presented.
 

Poster Session
6:00 PM-8:00 PM, Tuesday, March 24, 2009 Salt Palace Convention Center -- Hall 1, Poster

Division of Computers in Chemistry

The 237th ACS National Meeting, Salt Lake City, UT, March 22-26, 2009