Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IRintensities of several triatomic bromine compounds of known or potential importance in stratospheric ozonedepletion chemistry have been determined using the CCSD(T) electron correlation method in conjunctionwith a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in thepresent study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br20, BrBrO, BrCN, BrNC, C1OBr, CIBrO, andBrC10. Very accurate isomeric energy differences have also been determined at the CCSD(T) level withatomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with anormal neutral Lewis dot structure is the lowest energy form, with the single exception that FBrO is predictedto be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is morestable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistentwith this observation, the energy of the last three molecules given above increases in the order C1OBr

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