The HOO–SO 3 radical complex: ab initio and density-functional study

Abstract

The electronic structure and thermochemical stability of the HOO–SO 3 complex is studied using both second-order Møller–Plesset perturbation theory (MP2) and the B3LYP density-functional theory (DFT) method. The calculated dissociation energies of the complex are 10.25 and 11.51 kcal mol −1 at the G3(MP2) and G3 levels, respectively. Anharmonic OH stretching frequencies of the HO 2 moiety along with the frequency shifts upon complex formation are calculated at the MP2/6-311++G(2df,2p) and B3LYP/6-311++G(2df,2p) levels, and also AIM analyses of the MP2 and Kohn–Sham densities were performed. Theoretical data strongly encourage performing of matrix-isolation studies of the title complex and its spectroscopic identification.