Emambocus Shëyhaane A, Rhyman Lydia, Ramasami Ponnadurai
Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit 80837, Mauritius.
Department of Chemical Sciences, University of Johannesburg, PO Box 17011, Doornfontein, Johannesburg 2028, South Africa.
ACS Omega. 2020 Jan 22;5(4):1822-1831. doi: 10.1021/acsomega.9b03061. eCollection 2020 Feb 4.
A microhydration study of sulfur mustard (SM) was carried out using M06-2X, B3LYP, B3LYP-D3, and MP2 levels of theory with the 6-311++G(2d,2p) basis set. The changes in energetics, structural parameters and vibrational wavenumbers following the addition of up to three discrete water molecules to SM were analyzed. We observed slight changes in the geometry of SM upon microhydration. The stability of hydrated clusters is due to weak C-H···O-H hydrogen bonds. The free energy change for the formation of the clusters is positive at room temperature and becomes exergonic when the temperature decreases. The infrared stretchings of C-Cl of SM and O-H of water are redshifted upon the addition of water molecules. The findings from this work add to the literature of hydrated SM and can be useful in its detection and subsequent destruction.
使用M06 - 2X、B3LYP、B3LYP - D3和MP2理论水平以及6 - 311++G(2d,2p)基组对硫芥（SM）进行了微水合研究。分析了向SM中添加多达三个离散水分子后能量学、结构参数和振动波数的变化。我们观察到微水合作用下SM的几何结构有轻微变化。水合簇的稳定性归因于弱的C - H···O - H氢键。在室温下，簇形成的自由能变化为正，而当温度降低时变为放能反应。添加水分子后，SM的C - Cl红外伸缩振动和水的O - H红外伸缩振动发生红移。这项工作的研究结果丰富了水合SM的文献，可用于其检测及后续销毁。
