Nonempirical calculations of potential-energy surfaces for nucleophilic addition of H⁻ and F⁻ to an acetylene molecule

Abstract

The minimal energy paths for the nucleophilic addition of a hydride ion (H⁻) and a fluoride ion (F⁻) to a molecule of acetylene (A) have been calculated with the use of 3–21++G and 3–21+G double basis sets in the framework of the Hartree-Fock-Roothaan method. The values of the total energies of the reactants, transition states, and products have been refined by means of calculations with more complete basis sets [6–31++G// 3–21++G and 6–31++G*//3–21++G for reaction (1); 6–31+G*//3–21+G and 6–31++G**//3–21+G for reaction (2)] and by taking into account the correlation energy for reaction (1) in the framework of the SCEP/6–31++*//3–21++G method. It has been established that the activation energy of reaction (2) is 15.94 kJ/mole lower than that for reaction (1), that reaction (1) is exothermic, and that the enthalpy change accompanying reaction (2) is close to zero. The character of the distribution of the electron density along the minimal energy paths of both reactions has been analyzed, and the differences appearing as a result of the replacement of the soft nucleophile H⁻ by the harder nucleophile F⁻ have been ascertained. The results of the calculations have been compared with the results available in the literature for reaction (1).