A b i n i t i o calculations on the structure and nature of the hydrogen bonded complex H2S ⋅⋅⋅ HF

A b initio calculations employing an extended basis set and correlation energy estimates at the MP2 (second order Möller–Plesset) level have been used to estimate the binding energy, minimum energy S ...F distance, and minimum energy bisector angle θ (angle between the twofold axis of H2S and the S ...F line) for the hydrogen bonded complex H2S ... HF. The calculated distance and bisector angle θ are in reasonable agreement with experiment; the calculated binding energy can be used to provide a good estimate of the (as yet unknown) experimental value. Morokuma component analyses and simple electrostatic (molecular mechanics) calculations have been carried out on the complex as a function of bisector angle and they demonstrated that, despite suggestions to the contrary, the H2S ... HF bisector angle is predominantly determined by the electrostatic energy.