Ab initio molecular orbital calculations on LiPO2 and LiClO2 charge-transfer complexes: geometries and vibrational frequencies

Abstract

HF-SCF calculations are reported for the ions PO2− and ClO2− and for the charge-transfer complexes LiPO2 and LiClO2. Ab initio calculations indicate that the association between PO2− and ClO2− with the lithium atom depends on the position of the metal with respect to the anionic group and may occur in either bidentate or monodentate fashion. C2v and Cs symmetry structures were found to be stationary points on the total energy surfaces; the C2v bidentate form is the most stable equilibrium structure. Monodentate isomers of Cs and C2v symmetry were also characterized. Vibrational frequencies of the anions and of the C2v bidentate forms were computed.