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Tunable terahertz laser vibration−rotation-tunneling spectroscopy has been employed to characterize the structure and hydrogen bond network rearrangement dynamics of a cage form of the water hexamer having eight hydrogen bonds. The isolated clusters are produced in a pulsed supersonic slit jet. Striking similarities are found between the structure and the average interoxygen distance RO-O (2.82 A) of the hexamer cage and those of the basic unit of ice VI. The hybrid perpendicular band of b- and c-types is observed near 2.491 THz (83.03 cm-1) and rationalized to originate from the torsional motions of the two single-donor single-acceptor monomers about their donor hydrogen bonds, thereby causing changes in the dipole moments from each monomer to be orthogonal to each other as well as to be perpendicular to the approximate symmetry a-axis. Triplet spectral patterns accompanying each rovibrational transition with line spacings of 1.9 MHz and intensity ratios of 9:6:1 are attributed to the degenerate quantum ...

Terahertz Laser Vibration−Rotation Tunneling Spectroscopy and Dipole Moment of a Cage Form of the Water Hexamer