Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μm out-of-plane librational vibration.
We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm(-1) and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is ~524 cm(-1). Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.
Department of Chemistry, University of California, Berkeley, California 94705, USA.
William T S
WT
Cole
Department of Chemistry, University of California, Berkeley, California 94705, USA.
Ray S
RS
Fellers
Department of Chemistry, University of California, Berkeley, California 94705, USA.
Mark R
MR
Viant
Institut Charles Gerhardt UMR5253 CC15.01, CNRS and Universite Montpellier, 34095, Montpellier, Cedex 05, France.
Claude
C
Leforestier
Department of Chemistry, University of California, Berkeley, California 94705, USA.
Richard J
RJ
Saykally