Orientational effects in the direct Cl~- + CH_3Cl S_N2 reaction at elevated collision energies: hard-ovoid line-of-centers collision model

摘要

The hard-sphere line-of-centers collision model can be extended analytically to include the orientational dependence of both the energy barrier and the critical distance of approach. This hard-ovoid line-of-centers model is applied to the translational activation of the bimolecular nucleophilic substitution (S_N2) reaction, Cl~- + CH_3Cl -> ClCH_3 + Cl~-, for which a direct reaction mechanism was found in recent classical trajectory calculations. The model is compared with recent experiments and the classical trajectory calculations.