The rotational spectrum of H2SHI and an investigation by ab initio calculations of the origins of the observed doubling of rotational transitions in both H2SHI and H2SF2

The rotational spectrum of the complex H2S.HI observed with a pulsed-jet, Fourier-transform microwave spectrometer shows that each rotational transition is split into a closely spaced doublet, a pattern similar to that observed earlier for the halogen-bonded complex H2S.F-2. The origin of the doubling has been investigated by means of ab initio calculations conducted at the CCSD(T)(F12*)/ccpVDZ-F12 level. Two paths were examined by calculating the corresponding energy as a function of two angles. One path involved inversion of the configuration at S through a planar transition state of C2v symmetry via changes in the angle. between the C2 axis of H2S and the line joining the H and I nuclei [the potential energy function V(phi)]. The other was a torsional oscillation. about the local C2 axis of H2S that also exchanges the equivalent H nuclei [the potential energy function V(phi)]. The inversion path is slightly lower in energy and much shorter in arc length and is therefore the favored tunneling pathway. In addition, calculation of V(phi) for the series of hydrogen- and halogen-bonded complexes H2S.HX (X = F, Cl, or Br) and H2S.XY (XY = C(l)2, Br-2, ClF, BrCl, or ICl) at the same level of theory revealed that doubling is unlikely to be resolved in these, in agreement with experimental observations. The barrier heights of the V(.) of all ten complexes examined were found to be almost directly proportional to the dissociation energies D-e.