Novel bromine oxyfluorides:: structures, thermochemistry and electron affnities of BrOFn/BrOF-n (n = 1-5)

Four selected density functional theory (DFT) and hybrid Hartree-Fock/DFT methods have been used to carry out an investigation of the molecular structures, thermochemistry and the neutral-anion energy separations of the bromine oxygen. uorides BrOFn/BrOFn- (n = 1 - 5). Double-xi plus polarization quality basis sets augmented with the diffuse functions, labelled as DZP++0, were adopted. Thirty-four stationary points have been located on their potential energy hypersurfaces. Several previously unknown and novel structures are discovered in this research. For example, a beautiful, nearly octahedral C-4v structure is predicted to be a local minimum for BrOF5. Most global minima are found to be Br-centred, O-terminal structures, except for OBrF5, which has a higher energy than Br(OF)F-4 by similar to 6 kcal mol(-1). The adiabatic electron affnities (EAad) with ZPVE correction are predicted by BP86 to be 3.46 eV (BrOF), 3.90 eV (BrOF2), 4.02 eV ( BrOF3), 6.23 eV ( BrOF4) and 5.04 eV ( BrOF5). Except for BrOF4, these EAad values are smaller than those for the corresponding Br(2)Fn, BrC1Fn, and BrFn+1 species. The first fluorine dissociation energies for the BrOFn and BrOFn- ( n = 1 - 5) species are reported.