Тонкие химические технологии (Dec 2012)
Non-empirical calculations of minimal energetic ways of addition of H<sub>2</sub>F<sub>2</sub> and H<sub>2</sub>Cl<sub>2</sub> molecules to acetylene and methylacetylene molecules
Abstract
Surfaces of potential energy of gas phase addition reactions of H2F2 and H2Cl2 molecules to acetylene and methyl acetylene molecules were examined. An ab initio calculation of H2F2 and H2Cl2 molecules was carried out. A non-empirical Hartree-Fock-Roothaan method, 6-31 ++G** basis, taking into account electronic correlation in MP2 approximation (Møller-Plesset 2nd order) and Gaussian–03 software were used. Reaction heats and activation energies were calculated. It was established that addition of H2F2 and H2Cl2 molecules to a methyl acetylene molecule according to Markovnikov’s rule with the formation of 2-fluoropropene and HF and 2-chloropropene and HCl respectively is more advantageous both kinetically and thermodynamically.
