Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 119, Issue 17, Pages 8927-8937Publisher
AMER INST PHYSICS
DOI: 10.1063/1.1614774
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We report the measurement and analysis of 64 new K-a=0<--0,1 and K-a=1<--0,1 transitions of (H2O)(2) and 16 new K-a=0<--0 transitions of (D2O)(2) by terahertz laser vibration-rotation-tunneling spectroscopy of a planar supersonic expansion between 140.5 and 145.5 cm(-1). The transitions in both isotopomers correspond to A(') vibrations assigned to the hydrogen bond stretch (translational) and donor torsion overtone vibrations. The interchange splitting is 56.3 GHz in K-a=0 of the excited state of (H2O)(2), nearly 3 times the value of the ground state, and the bifurcation tunneling splitting is 1.8 GHz, over 2 times the value of the ground state. We compare the existing experimental spectra with calculations on state-of-the-art intermolecular potential energy surfaces and critically review the vibrational assignments reported in the literature. We show that the discrepancy between theory and experiment regarding the assignment of the feature near 103 cm(-1) can be resolved by considering E-2-->E-1 transitions, which had not been considered previously. (C) 2003 American Institute of Physics.
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