The molecular structures and the neutral-anion energy separations of the BrOnF/BrOnF- (n=2,3) species have been investigated using four density functional theory (DFT) methods. The FBrOO and FBrOOO chain structures are found to be the global minima for BrOnF/BrOnF- (n=2,3) species. The adiabatic electron affinities (EA(ad)) are predicted to be 4.75 eV for FBrOO and 4.02 eV for FBrOOO (with the BP86 method). The thermodynamically favored dissociation channel for BrOnF/BrOnF- (n=2,3) species is O-2 ((3)Sigma(-)(g))+(BrF/BrF- or OBrF/OBrF-). (C) 2007 Elsevier B.V. All rights reserved.