Structures and internal dynamics of diphenylether and its aggregates with water
Mariyam Fatima, Dominique Maué, Cristóbal Pérez, Denis S. Tikhonov, Dominic Bernhard, Anke Stamm, Chris Medcraft, Markus Gerhards, Melanie Schnell
Abstract
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.