Chemical Bonding in XeF2, XeF4, KrF2, KrF4, RnF2, XeCl2, and XeBr2: From the Gas Phase to the Solid State
Chemical Bonding in XeF2, XeF4, KrF2, KrF4, RnF2, XeCl2, and XeBr2: From the Gas Phase to the Solid State
复制标题
XeF2、XeF4、KrF2、KrF4、RnF2、XeCl2 和 XeBr2 中的化学键：从气相到固态
DOI：
10.1021/jp9825516
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发表时间：
1998
影响因子：
2.9
通讯作者：
Qianer Zhang
中科院分区：
文献类型：
--
作者：
M. Liao;Qianer Zhang
本文系统地研究了一系列惰性气体卤化物在气相和固相中的化学键。晶化环境用截止型Madelung势模拟。测定了它们的几何构型、离解能、力常数、生成热和升华热。计算结果与已有的实验数据吻合较好。晶场模型能够再现观察到的气相和固体之间的所有显著差异。KrF4、XeCl2和XeBr2被预测为对分子解离相当不稳定。二卤化物的稳定性顺序为KrF2≪XeF2和XeF2≫XeCl2≈XeBr2。计算出的趋势解释了这样一个事实，即只有较重的稀有气体才能形成化合物，而且配体的电负性必须很大。外极化轨道在成键过程中起着重要作用。相对论效应对分子性质的影响为负。
This paper presents a systematic investigation of chemical bonding in a series of noble-gas halides in both the gas phase and the solid state. The crystalline environment was simulated by a cutoff type Madelung potential. Geometries, dissociation energies, force constants, and enthalpies of formation and of sublimation were determined. The calculated properties are in good agreement with available experimental data. The crystal field model is capable of reproducing all significant differences observed between the gas phase and the solid state. KrF4, XeCl2, and XeBr2 are predicted to be rather unstable against molecular dissociation. The stabilities of the dihalides follow the order KrF2 ≪ XeF2 < RnF2 and XeF2 ≫ XeCl2 ≈ XeBr2. The calculated trends account for the fact that only the heavier noble gases form compounds and that the electronegativity of the ligand has to be large. The outer polarization orbitals play an important role in the bonding. Relativistic effects on the molecular properties are neglig...