Quantum-chemical interpretation of the difference in the field fragmentation of the molecular ions of dimethyl ether and dimethyl sulfide

The potential energy surfaces (PES) of the positive molecular ions of dimethyl ether and dimethyl sulfide were scanned by the LCAO-MO SCF method in the MINDO/3 valence approximation. On the PES of these radical-cations, apart from the minima corresponding to the equilbrium structures, each has a local minimum which belongs to a cyclic structure. The discovered differences in the stereochemical construction of the cyclic structures of the radical-cations (CH₃)₂O⁺'and (CH₃)₂S⁺' made it possible to explain features of the field fragmentation of their molecular ions. The effect of the external electric field of the ion source on the cyclization and fragmentation stages in the investigated radical-cations was traced.