Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride

• Main Authors: Calen J. Leverant, Chad W. Priest, Jeffery A. Greathouse, Mark K. Kinnan, Susan B. Rempe
• Format: Article
• Language: English
• Published: MDPI AG 2021-08-01
• Series: International Journal of Molecular Sciences
• Subjects: VX; aminolysis; base hydrolysis; decontamination; Hartree–Fock; density functional theory
• Online Access: https://www.mdpi.com/1422-0067/22/16/8653

Recently, lithium nitride (Li₃N) has been proposed as a chemical warfare agent (CWA) neutralization reagent for its ability to produce nucleophilic ammonia molecules and hydroxide ions in aqueous solution. Quantum chemical calculations can provide insight into the Li₃N neutralization process that has been studied experimentally. Here, we calculate reaction-free energies associated with the Li₃N-based neutralization of the CWA VX using quantum chemical density functional theory and ab initio methods. We find that alkaline hydrolysis is more favorable to either ammonolysis or neutral hydrolysis for initial P-S and P-O bond cleavages. Reaction-free energies of subsequent reactions are calculated to determine the full reaction pathway. Notably, products predicted from favorable reactions have been identified in previous experiments.