Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μ m libration

William T.S. Cole; Raymond S. Fellers; Mark R. Viant; Richard J. Saykally

doi:10.1063/1.4973418

Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μ m libration

William T.S. Cole, Raymond S. Fellers, Mark R. Viant, Richard J. Saykally^*

^*Corresponding author for this work

Biosciences

Research output: Contribution to journal › Article › peer-review

Abstract

Hydrogen bonds in solid and liquid water are formed and broken via librational vibrations, hence characterizing the details of these motions is vital to understanding these important dynamics. Here we report the measurement and assignment of 875 transitions comprising 6 subbands originating from out-of-plane librational transitions of the water pentamer-d₁₀ near 512 cm^-1. The precisely measured (ca. 1 ppm) transitions reveal bifurcation splittings of ∼1884 MHz, a ∼4000× enhancement over ground state splittings and 100× greater than predicted by theory. The pentamer is thus the third water cluster to display greatly enhanced bifurcation tunneling upon single quantum excitation of librational vibrations. From the intensity pattern of the observed transitions, the mechanism of bifurcation is established by comparison with theoretical predictions.

Original language	English
Article number	014306
Journal	Journal of Chemical Physics
Volume	146
Issue number	1
DOIs	https://doi.org/10.1063/1.4973418
Publication status	Published - 7 Jan 2017

Bibliographical note

Funding Information:
The Berkeley Terahertz project is supported by Chemical Structure, Dynamics, and Mechanisms-A Division of the National Science Foundation under Grant No. 1300723.The Berkeley Terahertz project is supported by Chemical Structure, Dynamics, and Mechanisms-A Division of the National Science Foundation under Grant No. 1300723.

Publisher Copyright:
© 2017 Author(s).

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1063/1.4973418

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title = "Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μ m libration",

abstract = "Hydrogen bonds in solid and liquid water are formed and broken via librational vibrations, hence characterizing the details of these motions is vital to understanding these important dynamics. Here we report the measurement and assignment of 875 transitions comprising 6 subbands originating from out-of-plane librational transitions of the water pentamer-d10 near 512 cm-1. The precisely measured (ca. 1 ppm) transitions reveal bifurcation splittings of ∼1884 MHz, a ∼4000× enhancement over ground state splittings and 100× greater than predicted by theory. The pentamer is thus the third water cluster to display greatly enhanced bifurcation tunneling upon single quantum excitation of librational vibrations. From the intensity pattern of the observed transitions, the mechanism of bifurcation is established by comparison with theoretical predictions.",

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AB - Hydrogen bonds in solid and liquid water are formed and broken via librational vibrations, hence characterizing the details of these motions is vital to understanding these important dynamics. Here we report the measurement and assignment of 875 transitions comprising 6 subbands originating from out-of-plane librational transitions of the water pentamer-d10 near 512 cm-1. The precisely measured (ca. 1 ppm) transitions reveal bifurcation splittings of ∼1884 MHz, a ∼4000× enhancement over ground state splittings and 100× greater than predicted by theory. The pentamer is thus the third water cluster to display greatly enhanced bifurcation tunneling upon single quantum excitation of librational vibrations. From the intensity pattern of the observed transitions, the mechanism of bifurcation is established by comparison with theoretical predictions.

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Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μ m libration

Abstract

Bibliographical note

ASJC Scopus subject areas

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