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The large amplitude tunneling motion of the HCl dimer has been directly studied with a tunable far‐infrared laser sideband/two‐dimensional free jet expansion spectrometer at hyperfine resolution. Rotationless tunneling rates for the three common chlorine isotopic forms are v(35–35) =463 979.2(1) MHz, v(35–37)=463 357.7(1) MHz, and v(37–37)=462 733.7(3) MHz. Both the rotational constants and hyperfine parameters indicate that the vibrationally averaged structure shows little variation within a given tunneling state, with both HCl bond angles giving an average projection on the a‐axis of 47° in all states with resolved hyperfine patterns.

Direct measurement of the HCl dimer tunneling rate and Cl isotope dependence by far-infrared laser sideband spectroscopy of planar supersonic jets