MCSCF study of the SN2 Menshutkin reaction in aqueous solution within the polarizable continuum model

The Menshutkin reaction NH3 + CH3 Cl --> CH3NH3+ + Cl- in aqueous solution is studied using the CASSCF method combined with the polarizable continuum model in a version that includes electrostatic, repulsion, and dispersion solute-solvent interactions. The solvent reaction field is inserted in the CASSCF Hamiltonian resorting to a mean-field approximation. The C-3v symmetry is maintained for all the geometries considered and the active space is generated distributing four electrons in four orbitals of al type. The results of the present study are in excellent agreement with recent ab initio calculations, which use both continuum and discrete solvation models, and with available experimental data. The analysis of the electronic structure of the transition state by the VB method explains the mechanism of this reaction in terms of a Linnett-type nonpaired spatial orbital representation as in a four-electron, three-center bonding unit.