THEORETICAL-STUDY OF CATION ETHER COMPLEXES - ALKALI-METAL CATIONS WITH 1,2-DIMETHOXYETHANE AND 12-CROWN-4/

Hartree-Fock and second-order perturbation theory methods were used to determine structures and binding enthalpies of complexes formed from a single alkali metal cation (Li+ through Cs+) and one or two 1,2-dime thoxyethane ligands or 12-crown-4. These calculations employed multipl e basis sets in order to determine the sensitivity of the results to t he completeness in the one-particle basis. The results are compared wi th recently reported collision-induced dissociation experimental findi ngs. In general, good agreement was found between the experimental and theoretical bond dissociation enthalpies, although for the heavier ca tions discrepancies of as much as 14 kcal/mol or more were uncovered. Possible reasons for these anomalies are discussed.