The intermolecular intetaction potential energy curves of DMF and benzene, DMF and toluene are calculated by means of smei-empirical SCF MO method-CNDO/2 and supermolecule approximation. The interiorrotation barrier of the bond between nitrogen atom and carbonyl carbon atom of DMF molecuie is also calculated.
The results show that the reaction is a multi - step complex one. Along the reaction path there are three transition states, two internal rotational barriers and four intermediates. The step IM3→TS2 is the rate - controlling step.
In order to give an instructive theoretical reference to experimental researchers, AM1 molecular orbital methods using the restricted Hartree- Fock (RHF) calculation have been applied to investigate the mechanism of the reaction of H_2O_2 with N_2O. The results show that this is a multi- step reaction.
High level calculations indicate ClNO2 can not transform to trans -ClONO directly, but a planar second-order saddle point (2SP) with a structure very close to isolated NO 2 + and Cl - has been obtained.