Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
Phys Chem Chem Phys. 2020 Dec 23;22(48):27966-27978. doi: 10.1039/d0cp04104a.
We report on a detailed multi-spectroscopic analysis of the structures and internal dynamics of diphenylether and its aggregates with up to three water molecules by employing molecular beam experiments. The application of stimulated Raman/UV and IR/UV double resonance methods as well as chirped-pulse Fourier transform microwave spectroscopy in combination with quantum-chemical computations yield the energetically preferred monomer and cluster geometries. Furthermore, the complex internal dynamics of the diphenylether monomer and the one-water clusters are analysed. In the cluster with three water molecules, water forms a cyclic structure similar to the isolated water trimer. The interactions ruling the structures of the higher-order water clusters are a combination of the ones identified for the two monohydrate isomers, with dispersion being a decisive contribution for systems that have a delicate energetic balance between different hydrogen-bonded arrangements of similar energy.
我们通过分子束实验报告了对二苯醚及其与多达三个水分子的聚集体的结构和内部动力学的详细多光谱分析。采用受激拉曼/紫外和红外/紫外双共振方法以及啁啾脉冲傅里叶变换微波光谱学与量子化学计算相结合，得出了能量上优先的单体和聚集体几何形状。此外，还分析了二苯醚单体和一水聚集体的复杂内部动力学。在包含三个水分子的聚集体中，水形成了类似于孤立水三聚体的环状结构。控制高阶水分子聚集体结构的相互作用是两种一水化物异构体所确定的相互作用的组合，其中色散对于不同氢键排列方式之间能量差异较小的系统是决定性的贡献。
