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Abstract

With the urgent need to provide an efficient and reliable protection for people from fatal chemical and biological weapons, our fundamental understanding of how toxins interact with filters is far from complete. The situation is further complicated by natural difficulties of performing experimental measurements with lethal toxins. Unlike experiments, computational modeling offers an attractive and safe yet reliable way of studying behavior of toxic agents on a variety of substrates at a great level of detail. Here, we report DFT-based quantum-chemical calculations of adsorption and decomposition of DMMP, sarin and soman on MoO₂ (011) surface. Our calculations show that MoO₂ strongly adsorbs toxic nerve agents and quickly decomposes them. Decomposition of DMMP on the MoO₂ (011) surface proceeds via the PO-CH₃ bond breaking and a formation of a surface methoxy group. The calculated activation barrier for this reaction is 131.5 kJ mol⁻¹. Unlike DMMP, decomposition of sarin and soman proceeds via the dealkylation reaction yielding propene and 3,3-dimethyl-1-butene, respectively. Decomposition of sarin requires a remarkably low energy (53.7 kJ mol⁻¹), whereas the similar reaction in soman requires 50 kJ mol⁻¹ more energy. We also make specific predictions to guide Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) experiments on sarin interaction with MoO₂ samples. We conclude that MoO₂ serves as an efficient substrate able of degrading toxins.