Thermodynamic characteristics of XeF₂ stepwise defluorination reaction have been studied using sophisticated methods of quantum chemistry. The set of standard enthalpies of formation for the XeF₂-related intermediates (radicals, ions) was obtained using approximation of coupled clusters level of theory [CCSD(T)/complete basis set extrapolation] with Peterson’s effective core potential correlation consistent basis sets for Xe. The standard enthalpy of formation for xenon monofluoride radical was determined to be Δ_fH°(XeF) = 15.4 kcal mol⁻¹ (298 K). The radical is formed in the first step of XeF₂ homolytic decomposition which requires 59.7 kcal mol⁻¹. The second step (XeF dissociation) is characterized by an extremely low binding energy (BDE(XeF) = 3.1 kcal mol⁻¹) explaining the high fluorinating potential of the xenon difluoride. An interpretation of low XeF stability was given in terms of MO – AO correlation diagrams. It was shown that the electronic structure of XeF radical may be described as combination of two main configurations, the first of them has a canonical set of MOs with single-occupied HOMO of antibonding character, whereas the second configuration is characterized by low-lying SOMO with main contributions from 5S AO of Xe and 2p_z AO of fluorine.

已经使用复杂的量子化学方法研究了XeF ₂逐步脱氟反应的热力学特征。XeF ₂相关中间体（自由基，离子）的标准形成焓集是使用理论上的耦合簇水平[CCSD（T）/完全基集外推法]和彼得森的有效核心电势相关一致基集获得的。薛 确定单氟化氙自由基的标准形成焓为_Δf H °（XeF ）= 15.4 kcal mol ^-1（298 K）。在XeF ₂均相分解的第一步中形成自由基，需要59.7 kcal mol ^-1。第二步骤（XeF解离）的特征在于极低的结合能（BDE（XeF）= 3.1 kcal mol ^-1），说明了二氟化氙的高氟化潜力。根据MO-AO相关图，对低XeF稳定性进行了解释。结果表明，XeF自由基的电子结构可以描述为两种主要构型的组合，它们中的第一个具有具有反键特征的单占领HOMO的规范MO组，而第二个构型的特征在于低位SOMO主要由Xe的5S AO和氟的2p _z AO贡献。