Terahertz VRT spectroscopy of the water hexamer-d 12 prism: Dramatic enhancement of bifurcation tunneling upon librational excitation

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

doi:10.1063/1.5006195

Title: Terahertz VRT spectroscopy of the water hexamer-d ₁₂ prism: Dramatic enhancement of bifurcation tunneling upon librational excitation

Journal Article · Thu Mar 01 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5006195· OSTI ID:1601175

Cole, William T. S. ^[1]; Farrell, James D. ^[2]; Sheikh, Akber A. ^[1];

^[3]; Fellers, Raymond S. ^[1]; Viant, Mark R. ^[1];

^[4];

^[1]

Univ. of California, Berkeley, CA (United States)
Chinese Academy of Sciences (CAS), Beijing (China). CAS Key Lab. of Soft Matter Physics, Beijing National Lab. for Condensed Matter Physics, Institute of Physics
Univ. of California, Berkeley, CA (United States); Ruhr-Univ. Bochum, North Rhine-Westphalia (Germany)
Univ. of Cambridge (United Kingdom)

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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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; 1300723.

OSTI ID:: 1601175

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 9; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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Title: Terahertz VRT spectroscopy of the water hexamer-d ₁₂ prism: Dramatic enhancement of bifurcation tunneling upon librational excitation