21st Annual Student Research Conference
Solution Phase Examination of the Potential Energy Surface for the Hydroperoxidolysis of a VX Simulant
Erin L. Futrell
Dr. Eric V. Patterson, Faculty Mentor
VX, O-ethyl S-(2-diisopropylamino)ethyl methylphosphonothiolate, is a nonvolatile liquid chemical warfare agent that is persistent in the environment. Chemical detoxification of VX requires cleavage of the P-S bond, which is readily accomplished by reaction of VX with alpha-nucleophiles. Previous computational studies on a VX simulant, O,S-dimethyl methylphosphonothiolate, revealed that reaction with hydroperoxide may occur via an unexpected intramolecular rearrangement. The previous study utilized gas phase geometries, while the energies were corrected for the effects of aqueous solvation. In order to understand whether the rearrangement is a gas-phase artifact, we have reexamined this reaction using density functional theory and a continuum solvation model. Stationary points were optimized for the attack of hydroperoxide opposite the methoxide ligand. In addition, we have used atom-centered density matrix propagation trajectory calculations to account for the effect of nuclear kinetic energy on the reaction mechanism.
Keywords: Computational, Chemistry, VX, Warfare Agent
Topic(s):Chemistry
Presentation Type: Oral Paper
Session: 32-4
Location: VH 1320
Time: 2:00