Density Functional Study of Structures and Electron Affinities of BrO(4)F/BrO(4)F(−)

The structures, electron affinities and bond dissociation energies of BrO(4)F/BrO(4)F(−) species have been investigated with five density functional theory (DFT) methods with DZP++ basis sets. The planar F-Br…O(2)…O(2) complexes possess (3)A′ electronic state for neutral molecule and (4)A′ state for the corresponding anion. Three types of the neutral-anion energy separations are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). The EA(ad) value predicted by B3LYP method is 4.52 eV. The bond dissociation energies D(e) (BrO(4)F → BrO(4-m)F + O(m)) (m = 1–4) and D(e)(−) (BrO(4)F(−) → BrO(4-m)F(−) + O(m) and BrO(4)F(−) → BrO(4-m)F + O(m)(−)) are predicted. The adiabatic electron affinities (EA(ad)) were predicted to be 4.52 eV for F-Br…O(2)…O(2) ((3)A′←(4)A′) (B3LYP method).