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Objective: to conduct quantum chemical modeling of a sulfur mustard molecule in an aqueous medium in the built–in parameter mode and in the mode of added molecules. After optimization by thermodynamic parameters, to study possible molecular and structural changes of mustard gas in the composition of the medium.
Methods. The Gaussian software package with the GaussView visualizer was used to construct and visualize the structure of the sulfur mustard molecule and its interaction with the aquatic environment. To carry out the calculation (calculation tipe FREQ), the standard Gaussian ab initio – Hartley-Fock (RHF) and post-Hartley-Fock (MP2) methods were chosen, which alternated with calculations based on the theory of the density function (DFT): B3LYP and B3LYP-FC. The semiempirical RPM6 method is used as a boundary factor.
Results. It is shown that only a comprehensive analysis of the state of the molecule makes it possible to identify the specific contribution of each type of interaction to the structure and properties of the molecule. In an aqueous environment, the mustard gas molecule has a high stability potential, but exposure to a real molecular environment leads to a change in polarizability, atomic charge, and dipole moment vector, and in the excited state of the molecule, one of the C1-Cl1 bonds is maximally activated, practically doubling its length.
Conclusions. Despite the very poor solubility of mustard gas in water, its intermolecular interaction with the medium leads to a redistribution of energy characteristics and the formation of a nonequilibrium polarizable state of the mustard molecule in the structure of the aquacomplex, possible further destruction with the formation of toxic products, including onium cations. Further development of the obtained results will make it possible to justify the choice of conditions for targeted activation of the mustard gas molecule for detoxification in aqueous media and body fluids.
Methods. The Gaussian software package with the GaussView visualizer was used to construct and visualize the structure of the sulfur mustard molecule and its interaction with the aquatic environment. To carry out the calculation (calculation tipe FREQ), the standard Gaussian ab initio – Hartley-Fock (RHF) and post-Hartley-Fock (MP2) methods were chosen, which alternated with calculations based on the theory of the density function (DFT): B3LYP and B3LYP-FC. The semiempirical RPM6 method is used as a boundary factor.
Results. It is shown that only a comprehensive analysis of the state of the molecule makes it possible to identify the specific contribution of each type of interaction to the structure and properties of the molecule. In an aqueous environment, the mustard gas molecule has a high stability potential, but exposure to a real molecular environment leads to a change in polarizability, atomic charge, and dipole moment vector, and in the excited state of the molecule, one of the C1-Cl1 bonds is maximally activated, practically doubling its length.
Conclusions. Despite the very poor solubility of mustard gas in water, its intermolecular interaction with the medium leads to a redistribution of energy characteristics and the formation of a nonequilibrium polarizable state of the mustard molecule in the structure of the aquacomplex, possible further destruction with the formation of toxic products, including onium cations. Further development of the obtained results will make it possible to justify the choice of conditions for targeted activation of the mustard gas molecule for detoxification in aqueous media and body fluids.
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2. Mazurek M., Witkiewicz Z., Popiel S., Śliwakowski M. Capillary gas chromatography – atomic emission spectroscopy – mass spectrometry analysis of sulphur mustard and transformation products in a block recovered from the Baltic Sea. Journal of Chromatography. 1 June, 2001. Vol. 919. Issue 1. P. 133 – 145. doi.org/10.1016/S0021-9673(01)00672-0
3. Hanaoka S., Nomura K., Wada T. Determination of mustard and lewisite related compounds in aban-doned chemical weapons (Yellow shells) from sources in China and Japan. Journal of Chromatography. 6 January, 2006. Vol. 1101. Issues 1-2. P. 268 – 277. doi.org/10.1016/j.chroma.2005.10.028
4. Medvedeva N., Polyak Yu., Kuzikova I., Orlova O., Zharikov G. The effect of mustard gas on the biological activity of soil. Environmental Research. March, 2008. Vol. 106. Issue 3. P. 289 – 295 doi.org/10.1016/j.envres.2007.04.003
5. Kornyakova V.V., Ashvits I.V., Muratov V.A. On the mechanism of action of mustard gas. Educational Bulletin "Consciousness". 2017. No. 8. P. 26 – 33.
6. Shefer T.V. Pathogenetic foundations of drug correction of early manifestations of acute resorptive action of mustard gas. Development of the concept of endotoxicosis: specialty 14.03.04 "Toxicology": author's abstract. diss. … doctor of medical sciences. St. Petersburg, 2015. 22 p.
7. Orlova O.G. Interaction of microorganisms with mustard gas hydrolysis products: author's abstract. diss. ... Cand. Biology. St. Petersburg, 2007. 20 p.
8. Ivanov A.I., Salomatin G.B., Skobaneva O.V. The Problem of Ecological Rehabilitation of Lake Mokhovoye Waters Polluted by Degradation Products of Toxic Substances in the Vicinity of Leonidovka Settlement, Penza Region. Theoretical and Applied Ecology. 2012. No. 4. P. 25 – 28.
9. Zaitseva T.B., Medvedeva N.G. The Influence of Mustard Gas Hydrolysis Products on the Development of Common Cyanobacteria Species. Principles of Ecology. 2017. No. 1 (22). P. 70 – 80.
10. Tyavlovskaya T.M., Tamelo V.F. Scientific and Practical Aspects of Cleaning Reservoirs from Chemical Warfare Agents. Science and Technology. 2011. No. 4. P. 48 – 51.
11. Klawohn S., Darby J.P., Kermode J.R. and all. Gaussian approximation potentials: Theory, software implementation and application examples Open Access. The Journal of Chemical Physics. 2023. Vol. 159. No. 17. doi.org/10.1063/5.0160898
12. Thomas du Toit D.F., Zhou Y., Deringer V.L. Hyperparameter optimization for atomic cluster expansion potentials.Journal of Chemical Theory and Computation. 2024. Vol. 20. No. 22. P. 10103 – 10113.
13. Montgomery Jr J.A. et al. A complete basis set model chemistry. VI. Use of density functional geometries and frequencies. The Journal of chemical physics. 1999. Vol. 110. No. 6. P. 2822 – 2827.
14. Budko E.V., Yamolsky L.M., Senchenko N.V. Mustard gas: structural features. Quantum-chemical modeling. Water: chemistry and ecology. 2025. No. 6. P. 20 – 27.
Budko E.V., Yampolsky L.M., Razinkova E.M. Quantum chemical modeling оf aqueous mustard gas solutions. Chemical Bulletin. 2025. 8 (4). 4. https://doi.org/10.58224/2619-0575-2025-8-4-4