Khriachtchev L, Pettersson M, Runeberg N, Lundell J, Rasanen M
Department of Chemistry, University of Helsinki, Finland.
Nature. 2000 Aug 24;406(6798):874-6. doi: 10.1038/35022551.
The noble gases have a particularly stable electronic configuration, comprising fully filled s and p valence orbitals. This makes these elements relatively non-reactive, and they exist at room temperature as monatomic gases. Pauling predicted in 1933 that the heavier noble gases, whose valence electrons are screened by core electrons and thus less strongly bound, could form stable molecules. This prediction was verified in 1962 by the preparation of xenon hexafluoroplatinate, XePtF6, the first compound to contain a noble-gas atom. Since then, a range of different compounds containing radon, xenon and krypton have been theoretically anticipated and prepared. Although the lighter noble gases neon, helium and argon are also expected to be reactive under suitable conditions, they remain the last three long-lived elements of the periodic table for which no stable compound is known. Here we report that the photolysis of hydrogen fluoride in a solid argon matrix leads to the formation of argon fluorohydride (HArF), which we have identified by probing the shift in the position of vibrational bands on isotopic substitution using infrared spectroscopy. Extensive ab initio calculations indicate that HArF is intrinsically stable, owing to significant ionic and covalent contributions to its bonding, thus confirming computational predictions that argon should form a stable hydride species with properties similar to those of the analogous xenon and krypton compounds reported before.
稀有气体具有特别稳定的电子构型,其价轨道的s和p轨道完全充满。这使得这些元素相对不活泼,在室温下以单原子气体形式存在。鲍林在1933年预测,较重的稀有气体,其价电子被内层电子屏蔽,因此束缚较弱,可能形成稳定的分子。1962年,六氟铂酸氙(XePtF6)的制备证实了这一预测,XePtF6是第一种含有稀有气体原子的化合物。从那时起,理论上已经预测并制备了一系列含有氡、氙和氪的不同化合物。尽管较轻的稀有气体氖、氦和氩在合适的条件下也有望发生反应,但它们仍然是元素周期表中最后三种已知没有稳定化合物的长寿命元素。在此我们报告,在固体氩基质中对氟化氢进行光解会导致氩氟氢化物(HArF)的形成,我们通过使用红外光谱探测同位素取代时振动带位置的变化对其进行了鉴定。大量的从头算计算表明,HArF本质上是稳定的,这归因于其键合中显著的离子和共价贡献,从而证实了计算预测,即氩应该形成一种稳定的氢化物物种,其性质与之前报道的类似氙和氪化合物的性质相似。