Abstract
A novel Raman jet-spectrometer is used to study the Fermi resonance between the OH bending overtone and OH stretching fundamental in small cyclic water clusters (H2O)n with n = 3, 4, 5. The new setup features a recirculating vacuum system which reduces the gas consumption by 2 to 3 orders of magnitude and enables long-term measurements of very weak Raman signals. Raman spectra measured from highly diluted expansions with unprecedented signal-to-noise ratio are presented and cluster-specific intensity ratios and effective coupling constants are derived using Markov-Chain Monte-Carlo methods, yielding a high probability for an almost "perfect" resonance for the tetramer and pentamer, i.e. a close frequency match of bend overtone and stretch fundamental with intensity ratios close to 1, but a larger coupling constant for the trimer, with best estimates close to W5 ≲ 50 cm-1 < W4 ≲ 60 cm-1 < W3 ≈ 65 cm-1.
Published Version (
Free)
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
