The strength of the OH-bend/OH-stretch Fermi resonance in small water clusters

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.