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

摘要

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-d(12) prism. These subbands reveal dramatically enhanced (ca. 1000x) 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. Published by AIP Publishing.