Intriguing Gold TrifluorideMolecular Structure of Monomers and Dimers: An Electron Diffraction and Quantum Chemical Study
Intriguing Gold TrifluorideMolecular Structure of Monomers and Dimers: An Electron Diffraction and Quantum Chemical Study
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有趣的三氟化金单体和二聚体的分子结构：电子衍射和量子化学研究
DOI：
10.1021/ja992638k
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发表时间：
2000
影响因子：
15
通讯作者：
M. Hargittai
中科院分区：
文献类型：
--
作者：
Balázs Réffy;M. Kolonits;A. Schulz;T. Klapötke;M. Hargittai
通过气相电子衍射和高级量子化学计算确定了单体和二聚体三氟化金AuF 3和Au 2F 6的分子几何结构。实验和计算都表明AuF 3的基态结构具有C2 v对称性，而不是三重对称性，具有一个较短和两个较长的Au−F键，并且由于一阶Jahn−Teller效应，基态结构几乎呈T形。CASSCF计算表明，三重态D3 h对称结构3A '位于1A 1对称基态之上约42 kcal/mol，而D3 h对称单线态1A'甚至比三重态高约13 kcal/mol。该分子具有典型的“墨西哥帽”型势能面，在帽边周围有三个相等的最低能量结构，由等高度的过渡结构隔开，约高于最低能量3.6 kcal/mol。还计算了过渡结构的几何形状。二聚体具有D2 h对称平面，卤素桥接的几何结构，具有良好的光学性能。
The molecular geometry of monomeric and dimeric gold trifluoride, AuF3 and Au2F6, has been determined by gas-phase electron diffraction and high-level quantum chemical calculations. Both experiment and computation indicate that the ground-state structure of AuF3 has C2v symmetry, rather than 3-fold symmetry, with one shorter and two longer Au−F bonds and an almost T-shaped form, due to a first-order Jahn−Teller effect. CASSCF calculations show the triplet D3h symmetry structure, 3A‘, to lie about 42 kcal/mol above the 1A1 symmetry ground state and the D3h symmetry singlet, 1A‘, even higher than the triplet state, by about a further 13 kcal/mol. The molecule has a typical “Mexican-hat”-type potential energy surface with three equal minimum-energy structures around the brim of the hat, separated by equal-height transition structures, about 3.6 kcal/mol above the minimum energy. The geometry of the transition structure has also been calculated. The dimer has a D2h symmetry planar, halogen-bridged geometry, w...