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.
Leverant, Calen J., et al. "Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride." International Journal of Molecular Sciences (Online), vol. 22, no. 16, Aug. 2021. https://doi.org/10.3390/ijms22168653
Leverant, Calen J., Priest, Chad W., Greathouse, Jeffery A., Kinnan, Mark K., & Rempe, Susan B. (2021). Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride. International Journal of Molecular Sciences (Online), 22(16). https://doi.org/10.3390/ijms22168653
Leverant, Calen J., Priest, Chad W., Greathouse, Jeffery A., et al., "Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride," International Journal of Molecular Sciences (Online) 22, no. 16 (2021), https://doi.org/10.3390/ijms22168653
@article{osti_1845385,
author = {Leverant, Calen J. and Priest, Chad W. and Greathouse, Jeffery A. and Kinnan, Mark K. and Rempe, Susan B.},
title = {Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride},
annote = {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.},
doi = {10.3390/ijms22168653},
url = {https://www.osti.gov/biblio/1845385},
journal = {International Journal of Molecular Sciences (Online)},
issn = {ISSN 1422-0067},
number = {16},
volume = {22},
place = {United States},
publisher = {MDPI},
year = {2021},
month = {08}}