ELECTRON DONOR-ACCEPTOR COMPLEXES OF I-2 WITH DIETHYL-ETHER AND DIETHYL SULFIDE - AN AB-INITIO MO STUDY

The charge-transfer complexes of I-2 with the n-donors diethyl ether a nd diethyl sulfide were studied at the Hartree-Fock and MP2 levels. Th e structures were fully optimized using the 3-21G(()) basis set as we ll as with effective core potentials. The calculations consistently yi eld a C-2v structure for the ether-I-2 complex, but an unsymmetrical f orm for the sulfide-I-2 complex. A natural bond orbital analysis and t he BSSE-corrected complexation energies reveal stronger interactions i n the sulfide complex. The computed orbital energies of the monomers a nd complexes reproduce the trends in experimentally observed vertical ionization potentials.