Abstract

Intermolecular interactions in bulk water are dominated by pairwise and non-pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested by precise low-frequency spectra of the water dimer up to 550 cm−1, the same does not hold for the three-body interactions. Here, we report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 using helium-nanodroplet isolation and free-electron lasers. By comparison to accompanying high-level quantum calculations, the experimentally observed intermolecular bands can be assigned. The transition frequencies of the degenerate translation, the degenerate in-plane and the non-degenerate out-of-plane libration, as well as additional bands of the out-of-plane librational mode are reported for the first time. These provide a benchmark for state-of-the-art water potentials and dipole-moment surfaces, especially with respect to three-body interactions.

Department(s)

Chemistry

Publication Status

Open Access

Comments

National Science Foundation, Grant CHE‐1664998

Keywords and Phrases

helium nanodroplets; vibrational spectroscopy; water cluster; water potential

International Standard Serial Number (ISSN)

1521-3773; 1433-7851

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2024 Wiley; Gesellschaft Deutscher Chemiker, All rights reserved.

Publication Date

06 Jul 2020

PubMed ID

32307809

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