Materials Structure and Modeling Research Group of the Hungarian Academy of Sciences, Budapest University of Technology and Economics, P.O. Box 91, 1521 Budapest, Hungary.
Inorg Chem. 2010 Mar 15;49(6):2816-21. doi: 10.1021/ic902196t.
The molecular geometries of VCl2 and VCl3 have been determined by computations and gas-phase electron diffraction (ED). The ED study is a reinvestigation of the previously published analysis for VCl2. The structure of the vanadium dichloride dimer has also been calculated. According to our joint ED and computational study, the evaporation of a solid sample of VCl2 resulted in about 66% vanadium trichloride and 34% vanadium dichloride in the vapor. Vanadium dichloride is unambiguously linear in its 4Sigma(g)+ ground electronic state. For VCl3, all computations yielded a Jahn-Teller-distorted ground-state structure of C(2v) symmetry. However, it lies merely less than 3 kJ/mol lower than the 3E'' state (D(3h) symmetry). Due to the dynamic nature of the Jahn-Teller effect in this case, rigorous distinction cannot be made between the planar models of either D(3h) symmetry or C(2v) symmetry for the equilibrium structure of VCl3. Furthermore, the presence of several low-lying excited electronic states of VCl3 is expected in the high-temperature vapor. To our knowledge, this is the first experimental and computational study of the VCl3 molecule.
VCl2 和 VCl3 的分子几何形状已经通过计算和气相电子衍射（ED）确定。ED 研究是对以前发表的 VCl2 分析的重新研究。还计算了二聚体的结构。根据我们的 ED 和计算研究，VCl2 固体样品的蒸发导致蒸气中约 66%的三氯化钒和 34%的二氯化钒。在其 4Sigma(g)+基态电子态中，VCl2 明确呈线性。对于 VCl3，所有计算都得到了 Jahn-Teller 畸变的 C(2v)对称基态结构。然而，它仅仅比 3E''态（D(3h)对称）低不到 3 kJ/mol。由于 Jahn-Teller 效应在这种情况下的动态性质，不能严格区分 VCl3 平衡结构的 D(3h)对称或 C(2v)对称的平面模型。此外，预计在高温蒸气中存在 VCl3 的几个低能激发电子态。据我们所知，这是对 VCl3 分子的首次实验和计算研究。
