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

Cohen, R. C. and Busarow, Kerry L. and Laughlin, K. B. and Blake, Geoffrey A. and Havenith, M. and Lee, Y. T. and Saykally, R. J. (1988) Tunable far infrared laser spectroscopy of van der Waals bonds: Vibration–rotation–tunneling spectra of Ar–H2O. Journal of Chemical Physics, 89 (8). pp. 4494-4504. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:COHjcp88

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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.


Item Type:Article
Additional Information:Copyright © 1988 American Institute of Physics. Received 31 May 1988; accepted 27 June 1988. This work was supported by the Director, Office of Energy Research, Office of Basic Sciences, Chemical Sciences Division of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098. The FIR laser system was funded by the National Science Foundation (Grant No. CHE-8612296) and by the Army Research Office University Research Instrumentation Program (Grant No. DAAL03-86-G-0184). [G.A.B. was a] Berkeley Miller Postdoctoral Fellow.
Subject Keywords:ARGON COMPLEXES, WATER, VIBRATIONAL STATES, ROTATIONAL STATES, ADDUCTS, ARGON, INFRARED SPECTRA, MOLECULAR STRUCTURE, LASER SPECTROSCOPY
Record Number:CaltechAUTHORS:COHjcp88
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:COHjcp88
Alternative URL:http://dx.doi.org/10.1063/1.454789
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10710
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:04 Jun 2008
Last Modified:26 Dec 2012 10:04

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