A systematic study of neutral and charged 3d-metal trioxides and tetraoxides

Using density functional theory with generalized gradient approximation, we have performed a systematic study of the structure and properties of neutral and charged trioxides (MO 3 ) and tetraoxides (MO 4 ) of the 3d-metal atoms. The results of our calculations revealed a number of interesting features when moving along the 3d-metal series. (1) Geometrical configurations of the lowest total energy states of neutral and charged trioxides and tetraoxides are composed of oxo and/or peroxo groups, except for CuO 3 − and ZnO 3 − which possess a superoxo group, CuO 4 + and ZnO 4 + which possess two superoxo groups, and CuO 3 + , ZnO 3 + , and ZnO 4 − which possess an ozonide group. While peroxo groups are found in the early and late transition metals, all oxygen atoms bind chemically to the metal atom in the middle of the series. (2) Attachment or detachment of an electron to/from an oxide often leads to a change in the geometry. In some cases, two dissociatively attached oxygen atoms combine and form a peroxo group or a peroxo group transforms into a superoxo group and vice versa. (3) The adiabatic electron affinity of as many as two trioxides (VO 3 and CoO 3 ) and four tetraoxides (TiO 4 , CrO 4 , MnO 4 , and FeO 4 ) are larger than the electron affinity of halogen atoms. All these oxides are hence superhalogens although only VO 3 and MnO 4 satisfy the general superhalogen formula.