Potential energy surface of the SOCl2+2H2O system

Thermodynamic parameters of elementary stages of thionyl chloride (SOCl2) hydrolysis in a gas phase proceeding with participation of water clusters, are calculated by a quantum-chemical method. The proposed mechanism included stages of formation of SOCl2 complexes with water dimers in which hydrolysis of S-Cl bond proceeds. Optimization of molecular geometry (search of transitive conditions) was done by a method of density functional (B3LYP//6-311++G(2d,2p)). For the found stationary points calculation of oscillatory frequencies was made and thermodynamic functions (TF) in harmonious approximation were estimated. For elementary stages of hydrolysis the transitive conditions were found and energy of activation was estimated. Results show that participation of water dimers leads to considerable decrease in energy of activation and acceleration of hydrolysis process.