Li⁺ Ion Attachment to Chloromethyl and Chlorofluoromethyl Peroxyl Radicals: Structures and Properties of CH_nCl_3−nO₂-Li⁺ and CF_nCl_3−nO₂-Li⁺ (n=0–3) Complexes

The structures and stabilities of these still experimentally unknown CH_nCl_3−nO₂-Li⁺ and CF_nCl_3−nO₂-Li⁺ ions have been theoretically investigated by ab initio molecular orbital theory and density functional theory (DFT) in conjunction with the 6-311G(d,p), 6-311+G(d,p), 6-311+G(2d,p) and 6-311+G(2df,2p) basis sets. The optimized geometries, chemical bonding and NBO analysis indicate that these complexes of CH_nCl_3−nO₂-Li⁺ and CF_nCl_3−nO₂- Li⁺ exist as ion-dipole molecules. The calculated affinity energies of these species exceed 41.9 kJ/mol, which are large enough to suggest the possibility that these title complexes could be detected as stable species in gas phase by Li⁺ ion attachment mass spectrometry.