Moreno Norberto, Restrepo Albeiro, Hadad C Z
Instituto de Química, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombia.
Phys Chem Chem Phys. 2018 Feb 14;20(7):5036-5045. doi: 10.1039/c7cp08085a.
We present a study of the isoelectronic PtNgF and [AuNgF] species with noble gas atoms (Ng = Kr, Xe, Rn) acting as links bridging the two noble metal atoms. The stability of the species is investigated using several thermodynamic, kinetic and reactivity indicators. The results are compared against [AuXe], which is thermodynamically unstable in the gas phase but is stabilized in the solid state to the point that it has been experimentally detected as AuXe (S. Seidel and K. Seppelt, Science, 2000, 290, 117-118). Our results indicate that improving upon [AuXe], these exotic combinations between the a priori non-reactive noble metals and noble gases lead to metastable species, and, therefore, they have the possibility of existing in the solid state under adequate conditions. Our calculations include accurate energies and geometries at both the CCSD/SDDALL and MP2/SDDALL levels. We offer a detailed description of the nature of the bonding interactions using orbital and density-based analyses. The computational evidence suggests partially covalent and ionic interactions as the stabilization factors.
我们展示了一项关于等电子体PtNgF和[AuNgF]物种的研究，其中稀有气体原子（Ng = Kr、Xe、Rn）作为连接两个贵金属原子的桥梁。使用多种热力学、动力学和反应性指标研究了这些物种的稳定性。将结果与[AuXe]进行了比较，[AuXe]在气相中热力学不稳定，但在固态中稳定到已通过实验检测到其为AuXe（S. 赛德尔和K. 泽佩尔特，《科学》，2000年，第290卷，第117 - 118页）。我们的结果表明，在[AuXe]的基础上，这些先验非反应性的贵金属与稀有气体之间的奇特组合会产生亚稳物种，因此，它们有可能在适当条件下以固态存在。我们的计算包括在CCSD/SDDALL和MP2/SDDALL水平下的精确能量和几何结构。我们使用基于轨道和密度的分析对键合相互作用的性质进行了详细描述。计算证据表明部分共价和离子相互作用是稳定因素。
