Tunable far-infrared laser spectroscopy of hydrogen bonds: The K a =0(u)→1(g) rotation–tunneling spectrum of the HCl dimer

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Abstract
The ground state K a =0(u)→1(g) b‐type subband of the rotation–tunneling spectrum of the symmetric 3 5Cl–3 5Cl, 3 7Cl–3 7Cl, and the mixed 3 5Cl–3 7Cl 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. Quadrupolehyperfine structure from the chlorine nuclei has been resolved. From the fitted rotational constants a (H3 5Cl)2 center‐of‐mass separation of 3.81 Å is derived for the K a =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 a b i n i t i o 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 t r a n stunneling 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°.