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Title: Terahertz VRT spectroscopy of the water hexamer-d 12 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.

Authors:
 [1];  [2];  [1]; ORCiD logo [3];  [1];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States)
  2. Chinese Academy of Sciences (CAS), Beijing (China). CAS Key Lab. of Soft Matter Physics, Beijing National Lab. for Condensed Matter Physics, Institute of Physics
  3. Univ. of California, Berkeley, CA (United States); Ruhr-Univ. Bochum, North Rhine-Westphalia (Germany)
  4. Univ. of Cambridge (United Kingdom)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1601175
Grant/Contract Number:  
AC02-05CH11231; 1300723.
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cole, William T. S., Farrell, James D., Sheikh, Akber A., Yönder, Öezlem, Fellers, Raymond S., Viant, Mark R., Wales, David J., and Saykally, Richard J. Terahertz VRT spectroscopy of the water hexamer-d 12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation. United States: N. p., 2018. Web. doi:10.1063/1.5006195.
Cole, William T. S., Farrell, James D., Sheikh, Akber A., Yönder, Öezlem, Fellers, Raymond S., Viant, Mark R., Wales, David J., & Saykally, Richard J. Terahertz VRT spectroscopy of the water hexamer-d 12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation. United States. https://doi.org/10.1063/1.5006195
Cole, William T. S., Farrell, James D., Sheikh, Akber A., Yönder, Öezlem, Fellers, Raymond S., Viant, Mark R., Wales, David J., and Saykally, Richard J. 2018. "Terahertz VRT spectroscopy of the water hexamer-d 12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation". United States. https://doi.org/10.1063/1.5006195. https://www.osti.gov/servlets/purl/1601175.
@article{osti_1601175,
title = {Terahertz VRT spectroscopy of the water hexamer-d 12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation},
author = {Cole, William T. S. and Farrell, James D. and Sheikh, Akber A. and Yönder, Öezlem and Fellers, Raymond S. and Viant, Mark R. and Wales, David J. and Saykally, Richard J.},
abstractNote = {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.},
doi = {10.1063/1.5006195},
url = {https://www.osti.gov/biblio/1601175}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 9,
volume = 148,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2018},
month = {Thu Mar 01 00:00:00 EST 2018}
}

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Cited by: 8 works
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Works referenced in this record:

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Works referencing / citing this record:

Highly localized H 2 O librational motion as a far-infrared spectroscopic probe for microsolvation of organic molecules
journal, January 2019


Thermodynamics and the potential energy landscape: case study of small water clusters
journal, January 2019