STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTIONS AT CARBON (SN2(C)) AND SILICON (SN2(Si)) IN TERMS OF AB INITIO, POTENTIAL ACTING ON AN ELECTRON IN A MOLECULE AND MOLECULAR FACE THEORY

The gas-phase identity bimolecular nucleophilic substitution reactions, Cl- + CH3Cl -> ClCH3 + Cl- and Cl- + SiH3Cl -> ClSiH3+ Cl-, are investigated in terms of the ab initio method, potential acting on an electron in a molecule (PAEM) and molecular face (MF) theory. The computations have been performed at the CCSD(T)/aug-cc-pVTZ//MP2/6-311++G(3df,3pd) and CISD/aug-cc-pVDZ level. Based on the ab initio calculation, according to the PAEM theory, the strength of a chemical bond during forming or rupturing may be characterized by the D-pb, which is a new physical quantity relating to the barrier height of the PAEM along a chemical bond. According to the MF theory, the interesting pictures of electron transfer and interpolarization effect between the reactants are clearly demonstrated to provide visualized spatial changing features of the MF for the title reactions along the IRC routes. The reason why [Cl center dot center dot center dot CH3 center dot center dot center dot Cl](-) is a high-energy transition state is also analyzed in comparison with the stable low-energy intermediate [Cl center dot center dot center dot SiH3 center dot center dot center dot Cl](-).