| Autor: |
Loru D; Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany., Steber AL; Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany., Pérez C; Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany., Obenchain DA; Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany., Temelso B; Division of Information Technology, College of Charleston, Charleston, South Carolina 29424, United States., López JC; Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid, Spain., Schnell M; Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany.; Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 1, D-24118 Kiel, Germany. |
| Abstrakt: |
Quantum tunneling is a fundamental phenomenon that plays a pivotal role in the motion and interaction of atoms and molecules. In particular, its influence in the interaction between water molecules and carbon surfaces can have significant implications for a multitude of fields ranging from atmospheric chemistry to separation technologies. Here, we unveil at the molecular level the complex motion dynamics of a single water molecule on the planar surface of the polycyclic aromatic hydrocarbon phenanthrene, which was used as a small-scale carbon surface-like model. In this system, the water molecule interacts with the substrate through weak O-H···π hydrogen bonds, in which phenanthrene acts as the hydrogen-bond acceptor via the high electron density of its aromatic cloud. The rotational spectrum, which was recorded using chirped-pulse Fourier transform microwave spectroscopy, exhibits characteristic line splittings as dynamical features. The nature of the internal dynamics was elucidated in great detail with the investigation of the isotope-substitution effect on the line splittings in the rotational spectra of the H 2 18 O, D 2 O, and HDO isotopologues of the phenanthrene-H 2 O complex. The spectral analysis revealed a complex internal dynamic showing a concerted tunneling motion of water involving its internal rotation and its translation between the two equivalent peripheral rings of phenanthrene. This high-resolution spectroscopy study presents the observation of a tunneling motion exhibited by the water monomer when interacting with a planar carbon surface with an unprecedented level of detail. This can serve as a small-scale analogue for water motions on large aromatic surfaces, i.e., large polycyclic aromatic hydrocarbons and graphene. |
