ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The ground state Ka =0(u)→1(g) b-type subband of the rotation–tunneling spectrum of the symmetric 35Cl–35Cl, 37Cl–37Cl, and the mixed 35Cl–37Cl hydrogen chloride dimers have been recorded near 26.3 cm−1 with sub-Doppler resolution in a continuous two-dimensional supersonic jet with a tunable far-infrared laser spectrometer. Quadrupole hyperfine structure from the chlorine nuclei has been resolved. From the fitted rotational constants a (H35Cl)2 center-of-mass separation of 3.81 A(ring) is derived for the Ka =1(g) levels, while the nuclear quadrupole coupling constants yield a vibrationally averaged angular structure for both tunneling states of approximately 20–25 deg for the hydrogen bonded proton and at least 70–75 deg for the external proton. This nearly orthogonal structure agrees well with that predicted by ab initio theoretical calculations, but the observed splittings and intensity alterations of the lines indicate that the chlorine nuclei are made equivalent by a large amplitude tunneling motion of the HCl monomers. A similar geared internal rotation tunneling motion has been found for the HF dimer, but here the effect is much greater. The ground state tunneling splittings are estimated to lie between 15–18 cm−1, and the selection rules observed indicate that the trans tunneling path dominates the large amplitude motion, as expected, provided the dimer remains planar. From the observed hyperfine constants, we judge the dimer and its associated tunneling motion to be planar to within 10°.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.455380
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