THEORETICAL-STUDY OF CATION ETHER COMPLEXES - THE ALKALI-METALS AND DIMETHYL ETHER/

The structures and binding enthalpies of a single alkali metal cation complexed with up through four dimethyl ether (DME) ligands were obtai ned with Hartree-Fock wave functions and second-order perturbation the ory, with consideration of core/valence correlation and relativistic e ffects. The basis sets used in this study included diffuse functions o n oxygen, in order to minimize undesirable basis set superposition err or, and polarization functions on all non-hydrogen atoms. The observed trends in complex formation energy along the sequence of cations are discussed and compared to the available experimental data obtained fro m collision-induced dissociation measurements. Minimum energy M+(DME)( 2) geometries are predicted to be Linear for the light metal complexes and bent for the heavy metal complexes.