A study of sulphur-containing molecules using Hartree-Fock, MP2 and DFT (hybrid) methodologies

The performance is examined of the B3P86 hybrid exchange-correlation function for a set of 21 sulphur-containing molecules. Optimized geometries, harmonic frequencies and mean molecular polarizabilities are presented, and compared with calculations to the HartreeFock and MP2 levels of theory, and with appropriate experimental results. The hybrid functional predicts geometries at a level comparable with the MP2 results; harmonic frequencies are in closer agreement with experimental results than either MP2 or Hartree-Fock method; mean molecular polarizabilities predicted by the hybrid functional appear to be substantially closer to experiment than those calculated by either of the other two methods.