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Issue 21, 2014
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The Raman spectrum of isolated water clusters

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Abstract

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

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Publication details

The article was received on 10 Oct 2013, accepted on 29 Nov 2013 and first published on 07 Jan 2014


Article type: Paper
DOI: 10.1039/C3CP54272F
Phys. Chem. Chem. Phys., 2014,16, 9849-9858
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    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

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