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Structure and torsional dynamics of the water octamer from THz laser spectroscopy near 215 μm.

Accepted version
Peer-reviewed

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Type

Article

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Authors

Cole, William TS 
Farrell, James D 
Wales, David J 
Saykally, Richard J 

Abstract

Clusters of eight water molecules play an important role in theoretical analysis of aqueous structure and dynamics but have proven to be challenging experimental targets. Here we report the high-resolution spectroscopic characterization of the water octamer. Terahertz (THz) vibration-rotation-tunneling (VRT) spectroscopy resolved 99 transitions with 1 part per million precision in a narrow range near 46.5 wave numbers, which were assigned to the h16 octamer via detailed isotope dilution experiments. Fitting to a semi-rigid symmetric top model supports predictions of two coexisting cuboidal structures and provides precise values for the changes in their rotational constants. Comparison with theory and previous spectroscopic data provides a characterization of the two structures and the observed torsional vibration and supports the prediction that the D2d symmetry structure is lower in energy than the S4 isomer.

Description

Keywords

0299 Other Physical Sciences, 0306 Physical Chemistry (incl. Structural)

Journal Title

Science

Conference Name

Journal ISSN

0036-8075
1095-9203

Volume Title

352

Publisher

American Association for the Advancement of Science (AAAS)