Li + Ion Attachment to Chloromethyl and Chlorofluoromethyl Peroxyl Radicals: Structures and Properties of CH n Cl 3 −n O 2 ‐Li + and CF n Cl 3− n O 2 ‐Li + ( n =0–3) Complexes

The structures and stabilities of these still experimentally unknown CH n Cl 3− n O 2 ‐Li + and CF n Cl 3− n O 2 ‐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 n Cl 3− n O 2 ‐Li + and CF n Cl 3− n O 2 ‐ 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.