Terahertz VRT spectroscopy of the water hexamer-d12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation

William T.S. Cole; James D. Farrell; Akber A. Sheikh; Öezlem Yönder; Raymond S. Fellers; Mark R. Viant; David J. Wales; Richard J. Saykally

doi:10.1063/1.5006195

Terahertz VRT spectroscopy of the water hexamer-d₁₂ prism: Dramatic enhancement of bifurcation tunneling upon librational excitation

William T.S. Cole, James D. Farrell, Akber A. Sheikh, Öezlem Yönder, Raymond S. Fellers, Mark R. Viant, David J. Wales, Richard J. Saykally^*

^*Corresponding author for this work

Biosciences

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

Abstract

Using diode laser vibration-rotation-tunneling spectroscopy near 15 Thz (500 cm^-1), we have measured and assigned 142 transitions to three a-type librational subbands of the water hexamer-d₁₂ prism. These subbands reveal dramatically enhanced (ca. 1000×) tunneling splittings relative to the ground state. This enhancement is in agreement with that observed for the water dimer, trimer, and pentamer in this same frequency region. The water prism tunneling motion has been predicted to potentially describe the motions of water in interfacial and confined environments; hence, the results presented here indicate that excitation of librational vibrations has a significant impact on the hydrogen bond dynamics in these macroscopic environments.

Original language	English
Article number	094301
Journal	Journal of Chemical Physics
Volume	148
Issue number	9
DOIs	https://doi.org/10.1063/1.5006195
Publication status	Published - 7 Mar 2018

Bibliographical note

Funding Information:
The Berkeley Terahertz project was previously supported by the Chemical Structure, Dynamics, and Mechanisms-A Division of the National Science Foundation under Grant No. 1300723. This project is currently supported by the CALSOLV collaboration, an affiliate program of RESOLV (Ruhr-Unversitaet Bochum). D.J.W. gratefully acknowledges financial support from the EPSRC.

Publisher Copyright:
© 2018 Author(s).

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

10.1063/1.5006195

Cite this

@article{195f976106fe4655b8f30027f38fe04b,

title = "Terahertz VRT spectroscopy of the water hexamer-d12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation",

abstract = "Using diode laser vibration-rotation-tunneling spectroscopy near 15 Thz (500 cm-1), we have measured and assigned 142 transitions to three a-type librational subbands of the water hexamer-d12 prism. These subbands reveal dramatically enhanced (ca. 1000×) tunneling splittings relative to the ground state. This enhancement is in agreement with that observed for the water dimer, trimer, and pentamer in this same frequency region. The water prism tunneling motion has been predicted to potentially describe the motions of water in interfacial and confined environments; hence, the results presented here indicate that excitation of librational vibrations has a significant impact on the hydrogen bond dynamics in these macroscopic environments.",

author = "Cole, {William T.S.} and Farrell, {James D.} and Sheikh, {Akber A.} and {\"O}ezlem Y{\"o}nder and Fellers, {Raymond S.} and Viant, {Mark R.} and Wales, {David J.} and Saykally, {Richard J.}",

note = "Funding Information: The Berkeley Terahertz project was previously supported by the Chemical Structure, Dynamics, and Mechanisms-A Division of the National Science Foundation under Grant No. 1300723. This project is currently supported by the CALSOLV collaboration, an affiliate program of RESOLV (Ruhr-Unversitaet Bochum). D.J.W. gratefully acknowledges financial support from the EPSRC. Publisher Copyright: {\textcopyright} 2018 Author(s).",

year = "2018",

month = mar,

day = "7",

doi = "10.1063/1.5006195",

language = "English",

volume = "148",

journal = "Journal of Chemical Physics",

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T1 - Terahertz VRT spectroscopy of the water hexamer-d12 prism

T2 - Dramatic enhancement of bifurcation tunneling upon librational excitation

AU - Cole, William T.S.

AU - Farrell, James D.

AU - Sheikh, Akber A.

AU - Yönder, Öezlem

AU - Fellers, Raymond S.

AU - Viant, Mark R.

AU - Wales, David J.

AU - Saykally, Richard J.

N1 - Funding Information: The Berkeley Terahertz project was previously supported by the Chemical Structure, Dynamics, and Mechanisms-A Division of the National Science Foundation under Grant No. 1300723. This project is currently supported by the CALSOLV collaboration, an affiliate program of RESOLV (Ruhr-Unversitaet Bochum). D.J.W. gratefully acknowledges financial support from the EPSRC. Publisher Copyright: © 2018 Author(s).

PY - 2018/3/7

Y1 - 2018/3/7

N2 - Using diode laser vibration-rotation-tunneling spectroscopy near 15 Thz (500 cm-1), we have measured and assigned 142 transitions to three a-type librational subbands of the water hexamer-d12 prism. These subbands reveal dramatically enhanced (ca. 1000×) tunneling splittings relative to the ground state. This enhancement is in agreement with that observed for the water dimer, trimer, and pentamer in this same frequency region. The water prism tunneling motion has been predicted to potentially describe the motions of water in interfacial and confined environments; hence, the results presented here indicate that excitation of librational vibrations has a significant impact on the hydrogen bond dynamics in these macroscopic environments.

AB - Using diode laser vibration-rotation-tunneling spectroscopy near 15 Thz (500 cm-1), we have measured and assigned 142 transitions to three a-type librational subbands of the water hexamer-d12 prism. These subbands reveal dramatically enhanced (ca. 1000×) tunneling splittings relative to the ground state. This enhancement is in agreement with that observed for the water dimer, trimer, and pentamer in this same frequency region. The water prism tunneling motion has been predicted to potentially describe the motions of water in interfacial and confined environments; hence, the results presented here indicate that excitation of librational vibrations has a significant impact on the hydrogen bond dynamics in these macroscopic environments.

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