The rotation-torsion energies in the electronic ground state of HSOH are obtained in variational calculations based on a newly computed ab initio CCSD(T)/aug-cc-pV(Q+d)Z potential energy surface. Using the concept of the reaction path Hamiltonian, as implemented in the program TROVE (theoretical rovibrational energies), the rotation-vibration Hamiltonian is expanded around geometries on the torsional minimum energy path of HSOH. The calculated values of the torsional splittings are in excellent agreement with experiment; the root-mean-square (rms) deviation is 0.0002cm1 for all experimentally derived splittings (with J40 and Ka4). The model provides reliable predictions for splittings not yet observed. The available experimentally derived torsion-rotation term values (with J40 and Ka4) are reproduced ab initio with an rms deviation of 1.2cm1 (0.7cm1 for J20), which is improved to 1.0cm1 (0.07cm1 for J20) in an empirical adjustment of the bond lengths at the planar trans configuration. The theoretical torsional splittings of HSOH are analyzed in terms of an existing semiempirical model for the rotation-torsion motion. The analysis explains the irregular variation of the torsional splittings with Ka that has been observed experimentally.

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