Observation of the low-frequency spectrum of the water dimer as a sensitive test of the water dimer potential and dipole moment surfaces
- Using the helium nanodroplet isolation setup at the ultrabright free‐electron laser source FELIX in Nijmegen (BoHeNDI@FELIX), the intermolecular modes of water dimer in the frequency region from 70 to 550 cm\(^{−1}\) were recorded. Observed bands were assigned to donor torsion, acceptor wag, acceptor twist, intermolecular stretch, donor torsion overtone, and in‐plane and out‐of‐plane librational modes. This experimental data set provides a sensitive test for state‐of‐the‐art water potentials and dipole moment surfaces. Theoretical calculations of the IR spectrum are presented using high‐level quantum and approximate quasiclassical molecular dynamics approaches. These calculations use the full‐dimensional ab initio WHHB potential and dipole moment surfaces. Based on the experimental data, a considerable increase of the acceptor switch and a bifurcation tunneling splitting in the librational mode is deduced, which is a consequence of the effective decrease in the tunneling barrier.
| Author: | Raffael SchwanGND, Chen QuORCiDGND, Devendra ManiGND, Nitish PalORCiDGND, Lex van der MeerGND, Britta RedlichGND, Claude LeForestierGND, Joel M. BowmanGND, Gerhard SchwaabGND, Martina HavenithORCiDGND |
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| URN: | urn:nbn:de:hbz:294-79298 |
| DOI: | https://doi.org/10.1002/anie.201906048 |
| Parent Title (German): | Angewandte Chemie International Edition |
| Publisher: | Wiley-VCH Verlag |
| Place of publication: | Weinheim |
| Document Type: | Article |
| Language: | English |
| Date of Publication (online): | 2021/03/05 |
| Date of first Publication: | 2019/07/27 |
| Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
| Tag: | IR spectroscopy; helium nanodroplets; potential surfaces; quantum calculations; water clusters |
| Volume: | 58 |
| Issue: | 37 |
| First Page: | 13119 |
| Last Page: | 13126 |
| Note: | Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich. |
| Institutes/Facilities: | Lehrstuhl für Physikalische Chemie II |
| Dewey Decimal Classification: | Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie |
| open_access (DINI-Set): | open_access |
| Licence (English): |  Creative Commons - CC BY-NC 4.0 - Attribution-NonCommercial 4.0 International |
