Theoretical study on the selectivity of the insertion xenon atom into hypohalous acids

• The three-body reactions are predicted to be the mainly decomposition channels of HOXeX/HXeOX.
• The H–Xe (HXeOX) and O–H (HOXeX) stretching modes are highly anharmonic.
• The electrostatic interaction is the main driving force for the formation of ionic (HXe)+(OX)− or (HO)+(XeX)−.

The structures, harmonic/anharmonic vibrational frequencies, stabilities and bondings of HOXeX/HXeOX (X = F, Cl, Br and I) were investigated. Both HXeOX/HOXeX were confirmed to be stable, and HOXeX is more stable thermodynamically than corresponding HXeOX. The two-body decomposition reactions of them are exothermic, while the three-body ones are endothermic. However, both of them are stabilized kinetically with respect to the two-/three-body decomposition reactions by enough highly energy barriers. The three-body reactions are predicted to be the mainly decomposition channels because of the lower energy barriers of TS2. The VSCF analysis shows that the H–Xe (HXeOX) and O–H (HOXeX) stretching modes are highly anharmonic and are very likely to be observed experimentally. The nature of the bondings in HXeOX/HOXeX were analyzed by QTAIM, LMO-EDA and Löwdin/NPA population methods, and found that the electrostatic interaction is the main driving force for the formation of ionic (HXe)+(OX)− or (HO)+(XeX)−.

HOXeX (X = F, Cl, Br and I) is more stable thermodynamically than corresponding HXeOX. Both of them are stabilized kinetically with respect to the two-/three-body decomposition reactions, while the three-body ones are predicted to be the mainly decomposition channels.Figure optionsDownload as PowerPoint slide