Issue 21, 2014

The Raman spectrum of isolated water clusters


Cold water oligomers (H2O)n and (D2O)n with n = 2–5 are assigned in spontaneous Raman scattering spectra of seeded rare gas expansions for the first time. Comparison with infrared spectra provides direct experimental insights into the hydrogen bond-mediated excitonic OH oscillator coupling, which is responsible for ultrafast energy transfer between water molecules, usually suppressed by isotopic dilution in femtosecond experiments for the condensed phase. The experimental coupling constants are compared to those in state-of-the-art full-dimensional water potential energy hypersurfaces, leaving room for improvement in the description of the coupled dynamics in water. Evidence for intensified Fermi resonance between OH stretching and OH bending motion beyond water trimers is collected.

Graphical abstract: The Raman spectrum of isolated water clusters

Supplementary files

Article information

Article type
10 Oct 2013
29 Nov 2013
First published
07 Jan 2014
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2014,16, 9849-9858

The Raman spectrum of isolated water clusters

K. E. Otto, Z. Xue, P. Zielke and M. A. Suhm, Phys. Chem. Chem. Phys., 2014, 16, 9849 DOI: 10.1039/C3CP54272F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity