Nucleophilic substitution reaction between some substituted benzyl chlorides and chloride ion has been investigated by ab initio and DFT methods. New calculated energy data are in better agreement with experimental data. The electronwithdrawing groups increase the energy barriers and the electron-donating groups decrease them. The changes of geometrical parameters and energy data are in good agreement with the results of atoms in molecules and natural bond orbital analyses. The relationship between Hammett coefficients and energy data (and geometry parameters) has been established and the q constant has been calculated for this reaction.

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The effects of solvent on S N 2 reaction between some substituted benzyl chlorides and chloride ion have been investigated by DFT and ab initio methods using the polarizabale continuum model. The activation energies are higher in the solution media relative to the gas phase and grow by the increase in the dielectric constant of solvent. The complexation energies in solution media are smaller than those in the gas phase and reduce with increasing the dielectric constant. The energy data are in good agreement with the geometrical parameters and substituent constants.