Mark Hoffmann is supported by a grant from The Theoretical and Computational Chemistry Program to perform theoretical studies of the structures and unimolecular reactions of fluoro- and oxyfluoro- substituted dioxiranes, diazirines and phosphaazirines. Hoffmann will perform ab initio theoretical calculations to characterize the relevant equilibrium structures of these compounds on the ground and low-lying excited state potential energy surfaces as well as to calculate a number of physical properties such as dipole moments, vibrational frequencies and electronic spectra. Thermodynamic stabilities of various isomers, and possible channels for isomerization and unimolecular decomposition will also be studied. Extensive use of dynamic electron correlation at relatively high levels and the use of extended polarized basis sets are necessary for the study of these compounds. In addition, the location of minima and transition states for these species will be performed using the multi-reference configuration interaction with single and double excitation (MR-CISD) in conjunction with a newly realized incomplete model space multi-configuration self consistent field (MCSCF) program.
The interest in these compounds arises from their use as powerful oxidants that may be effective as components of fuels, and the fact that some are precursors for radicals important in understanding stratospheric processes.
