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

Accepted version
Peer-reviewed

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Type

Article

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Authors

Cole, WTS 
Farrell, JD 
Sheikh, AA 
Fellers, RS 

Abstract

jats:pUsing 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.</jats:p>

Description

Keywords

51 Physical Sciences, 34 Chemical Sciences, 3406 Physical Chemistry

Journal Title

Journal of Chemical Physics

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

148

Publisher

AIP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/N035003/1)