Probing the Hydrogen Bonding in Microsolvated Clusters of Au-1,2(-)(Solv)(n) (Solv = C2H5OH, n-C3H7OH; n=1-3 for Au-; n=1 for Au-2(-))
Probing the Hydrogen Bonding in Microsolvated Clusters of Au-1,2(-)(Solv)(n) (Solv = C2H5OH, n-C3H7OH; n=1-3 for Au-; n=1 for Au-2(-))
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探讨 Au-1,2(-)(Solv)(n) 微溶剂化簇中的氢键 (Solv = C2H5OH, n-C3H7OH; Au- 为 n=1-3; Au-2(-) 为 n=1
DOI：
10.1021/acs.jpca.0c03746
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发表时间：
2020
影响因子：
2.9
通讯作者：
Liu Hongtao
中科院分区：
文献类型：
--
作者：
Wang Yongtian;Han Changcai;Fei Zejie;Dong Changwu;Liu Hongtao
采用阴离子光电子能谱和量子化学计算相结合的方法，对au1,2 - (Solv)n（Solv = C2H5OH,n- c3h7oh, Au - n= 1 - 3, Au2 - n= 1）在不同醇溶剂中进行了金阴离子的微溶剂化。通过计算与实验的比较，确定了这些簇的微溶剂化结构及其相应的中性物。在整体规律性方面，溶剂化数(n)的增加和碳链的延伸都能提高阴离子的稳定性。当≥2时，这些簇具有低能异构体，其中常规氢键（HBs）与非常规氢键（NHBs）竞争。NHBs在≤2和nis增加时占主导地位，反之亦然。有趣的是，各种理论计算表明，在乙醇分子的羟基H原子与Au -形成弱离子HB后，乙醇有反式和间扭式两种最低构象，可以在分子束中共存。一些理论方法还表明，间扭异构体比反式异构体更稳定，这表明金可能以类似氟的金间扭效应存在。
The microsolvation of gold anions in different alcohol solvents is demonstrated by the combination of anion photoelectron spectroscopy and quantum chemical calculations on the Au1,2–(Solv)n(Solv = C2H5OH,n-C3H7OH;n= 1–3 for Au–;n= 1 for Au2–). The microsolvation structures of these clusters and their corresponding neutrals are assigned by comparing calculations with experiments. In terms of overall regularity, the increasing solvation number (n) and carbon chain extension both can increase the stability of the anion. Whenn≥ 2, these clusters have low-energy isomers, where conventional hydrogen bonds (HBs) compete with nonconventional HBs (NHBs). NHBs are dominant whenn≤ 2 and whennis increased, vice versa. Interestingly, a variety of theoretical calculations show that after the hydroxy H atom of the ethanol molecule forms a weak ionic HB with Au–, there are two lowest conformations of ethanol, trans and gauche, which could be coexisting in the molecular beams. Some theoretical methods also suggest that the gauche isomer is more stable than the trans one, which indicates that Au–may exist as a gold gauche effect similar to fluorine.