Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

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

doi:10.1021/acs.jpca.8b05777

Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

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

^*Corresponding author for this work

Biosciences

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

Abstract

We report the assignment and analysis of 176 transitions belonging to a librational band of the (H₂O)₆ cage isomer near 525 cm^-1(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.

Original language	English
Pages (from-to)	7421-7426
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	122
Issue number	37
DOIs	https://doi.org/10.1021/acs.jpca.8b05777
Publication status	Published - 20 Sept 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 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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@article{eb5714027ecc4a26a31a9a72f9563695,

title = "Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics",

abstract = "We report the assignment and analysis of 176 transitions belonging to a librational band of the (H2O)6 cage isomer near 525 cm-1(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.",

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

year = "2018",

month = sep,

day = "20",

doi = "10.1021/acs.jpca.8b05777",

language = "English",

volume = "122",

pages = "7421--7426",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "37",

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TY - JOUR

T1 - Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage

T2 - Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

AU - Cole, William T.S.

AU - Yönder, Özlem

AU - Sheikh, Akber A.

AU - Fellers, Raymond S.

AU - Viant, Mark R.

AU - Saykally, Richard J.

AU - Farrell, James D.

AU - Wales, David 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 American Chemical Society.

PY - 2018/9/20

Y1 - 2018/9/20

N2 - We report the assignment and analysis of 176 transitions belonging to a librational band of the (H2O)6 cage isomer near 525 cm-1(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.

AB - We report the assignment and analysis of 176 transitions belonging to a librational band of the (H2O)6 cage isomer near 525 cm-1(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.

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U2 - 10.1021/acs.jpca.8b05777

DO - 10.1021/acs.jpca.8b05777

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AN - SCOPUS:85053356200

SN - 1089-5639

VL - 122

SP - 7421

EP - 7426

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 37

ER -

Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics

Abstract

Bibliographical note

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