Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μm out-of-plane librational vibration

Journal Article · Wed Oct 21 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4933116· OSTI ID:22493131

Cole, William T. S.; Fellers, Ray S.; Viant, Mark R.; Leforestier, Claude ^[1]

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1. Institut Charles Gerhardt UMR5253 CC15.01, CNRS and Universite Montpellier, 34095, Montpellier, Cedex 05 (France)

We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm{sup −1} and assigned to (H{sub 2}O){sub 2} libration-rotation-tunneling eigenstates. The band origin for the K{sub a} = 1 subband is ~524 cm{sup −1}. Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.

• OSTI ID: 22493131
• Journal Information: Journal of Chemical Physics, Vol. 143, Issue 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DIMERS
DISTURBANCES
EIGENSTATES
ENERGY LEVELS
EXCITATION
HYDROGEN
LASER SPECTROSCOPY
LEAST SQUARE FIT
PERTURBATION THEORY
ROTATION
SPECTRA
TUNNEL EFFECT
TUNNELING
WATER