State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Phys Chem Chem Phys. 2014 Mar 14;16(10):4771-7. doi: 10.1039/c3cp51851e.
We have combined photoelectron velocity-map imaging (VMI) spectroscopy and theoretical calculations to elucidate the geometry and energy properties of Aux(-)(Solv)n clusters with x = 1, 2; n = 1, 2; and Solv = H2O and CH3OH. Besides the blue-shifted vertical electron detachment energies (VDEs) of the complexes Au1,2(-)(Solv)n with the increase of the solvation number (n), we independently probed two distinct Au(-)(CH3OH)2 isomers, which combined with MP2/aug-cc-pVTZ(pp) calculations represent a competition between O···H-O hydrogen bonds (HBs) and Au···H-O nonconventional hydrogen bonds (NHBs). Complementary calculations provide the total binding energies of the low-energy isomers. Moreover, the relationship between the total binding energies and total VDEshift is discussed. We found that the Au1,2(-) anions exhibit halide-analogous behavior in microsolvation. These findings also demonstrate that photoelectron velocity map imaging spectroscopy with the aid of the ab initio calculations is an effective tool for investigating weak-interaction complexes.
我们结合光电子速度映射成像（VMI）光谱和理论计算，阐明了Aux（-）（Solv）n 簇（x = 1,2；n = 1,2；Solv = H2O 和 CH3OH）的几何形状和能量特性。除了复合物 Au1,2（-）（Solv）n 的垂直电子离解能（VDE）随着溶剂化数（n）的增加而蓝移外，我们还独立探测到两种不同的 Au（-）（CH3OH）2 异构体，与 MP2/aug-cc-pVTZ（pp）计算相结合，代表了 O···H-O 氢键（HB）和 Au···H-O 非常规氢键（NHB）之间的竞争。补充计算提供了低能异构体的总结合能。此外，还讨论了总结合能与总 VDEshift 之间的关系。我们发现 Au1,2（-）阴离子在微溶剂化中表现出类似卤化物的行为。这些发现还表明，借助从头算计算的光电子速度映射成像光谱是研究弱相互作用配合物的有效工具。
