A quantum chemical calculation of the potential energy surface in the formation of HOSO2 from OH + SO2

Abstract

Abstract The formation of HOSO 2 from OH and SO 2 has been thoroughly investigated using several different methods (MP2=Full, MP2=FC, B3LYP, HF and composite G∗ methods) and basis sets (6–31G(d,p), 6–31++G(d,p), 6–31++G(2d,2p), 6–31++G(2df,2p) and aug-cc-pVnZ). We have found two different possible transition state structures, one of which is a true transition state since it has a higher energy than the reactants and products (MP2=Full, MP2=FC and HF), while the other is not a true transition state since it has an energy which lies between that of the reactants and products (B3LYP and B3LYP based methods). The transition state structure (from MP2) has a twist angle of the OH fragment relative to the SO bond of the SO 2 fragment of −50.0°, whereas this angle is 26.7° in the product molecule. Examination of the displacement vectors confirms that this is a true transition state structure. The MP2=Full method with a larger basis set (MP2=Full/6–31++G(2df,2p)) predicts the enthalpy of reaction to be −112.8 kJ mol −1 which is close to the experimental value of −113.3 ± 6 kJ mol −1 , and predicts a rather high barrier of 20.0 kJ mol −1 . When the TS structure obtained by the MP2 method is used as the input for calculating the energetics using the QCISD/6–31++G(2df,2p) method, a barrier of 4.1 kJ mol −1 is obtained (ZPE corrected). The rate constant calculated from this barrier is 1.3 × 10 −13 cm 3 molecule −1 s −1 . We conclude that while the MP2 methods correctly predict the TS from a structural point of view, higher level energy corrections are needed for estimation of exact barrier height.