Supercritical water is not hydrogen bonded
- Thinking about water is inextricably linked to hydrogen bonds, which are highly directional in character and determine the unique structure of water, in particular its tetrahedral H-bond network. Here, we assess if this common connotation also holds for supercritical water. We employ extensive ab initio molecular dynamics simulations to systematically monitor the evolution of the H-bond network mode of water from room temperature, where it is the hallmark of its fluctuating three-dimensional network structure, to supercritical conditions. Our simulations reveal that the oscillation period required for H-bond vibrations to occur exceeds the lifetime of H-bonds in supercritical water by far. Instead, the corresponding low-frequency intermolecular vibrations of water pairs as seen in supercritical water are found to be well represented by isotropic van-der-Waals interactions only. Based on these findings, we conclude that water in its supercritical phase is not a H-bonded fluid.
| Author: | Philipp SchienbeinORCiDGND, Dominik MarxORCiDGND |
|---|---|
| URN: | urn:nbn:de:hbz:294-98994 |
| DOI: | https://doi.org/10.1002/anie.202009640 |
| Parent Title (German): | Angewandte Chemie International Edition |
| Publisher: | Wiley-VCH |
| Place of publication: | Hoboken, New Jersey |
| Document Type: | Article |
| Language: | English |
| Date of Publication (online): | 2023/05/22 |
| Date of first Publication: | 2020/08/04 |
| Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
| Tag: | ab initio calculations; hydrogen bonds; molecular dynamics; supercritical fluids; water |
| Volume: | 59 |
| Issue: | 42 |
| First Page: | 18578 |
| Last Page: | 18585 |
| Note: | Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich. |
| Institutes/Facilities: | Lehrstuhl für Theoretische Chemie |
| Dewey Decimal Classification: | Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie |
| open_access (DINI-Set): | open_access |
| faculties: | Fakultät für Chemie und Biochemie |
| Licence (English): |  Creative Commons - CC BY 4.0 - Attribution 4.0 International |
