Tunable far infrared laser spectroscopy of van der Waals bonds: Vibration–rotation–tunneling spectra of Ar–H2O

Abstract

The first high resolution spectra of a rare gas–H2O cluster have been observed using a tunable far infrared laser to probe the vibration–rotation–tunneling levels of Ar–H2O formed in a continuous planar supersonic jet. The high sensitivity of this spectrometer facilitated extensive measurements of two perpendicular subbands which are assigned to transitions from the ground state to the upper component of a hydrogen exchange tunneling doublet (c-type) at 21 cm^−1, and to vb1 =1+ (b-type) at 25 cm^−1, the lower tunneling component of a bending vibration which is perpendicular to the tunneling coordinate. The tunneling splitting is shown to be in the range 2.5–7 cm^−1 and the lower tunneling component of the excited bending vibration lies between 39 and 43 cm^−1 above the ground state of the complex. The experimentally determined center-of-mass separation (Rc.m. =3.75 Å) and harmonic stretching force constant (ks =0.0134 mdyn/Å) are compared to those of related first and second row hydrides. The large amplitude motions occurring within this complex make it difficult to establish its structure.