Journal of Chemical Physics, Vol.107, No.7, 2300-2307, 1997
The Obro C((2)A(2))(-X(B-2(1)) Absorption-Spectrum
The highly structured visible absorption spectrum of the bromine dioxide radical, OBrO, has been observed in the 15 500-26 000 cm(-1) region. The spectrum is dominated by a long progression in the Br-O symmetric stretching motion (nu(1)’) and a series of short progressions built on the bending mode (nu(2)’); there are no features associated with the excitation of the antisymmetric stretching mode (nu(3)’), The spectrum also contains numerous transitions originating from the (0,1,0) and (1,0,0) vibrational levels of the electronic ground state, X(B-2(1)), A simultaneous fit to all of the observed vibronic features yielded the frequencies nu(1) "=799.4 cm(-1), nu(2) "=317.5 cm(-1), omega w(1)=641.5 cm(-1) omega(2)’ = 210.7 cm(-1), and a band origin T-0 = 15 863 cm(-1). Franck-Condon simulations combined with ab initio calculations of the four lowest OBrO doubler electronic states identify the spectrum as arising from the C((2)A(2))<--X(B-2(1)) electronic transition.
Keywords:GAUSSIAN-BASIS SETS;MOLECULAR CALCULATIONS;CHLORINE PEROXIDE;TRANSITION;KINETICS;ATOMS;DECOMPOSITION;MECHANISM;RADICALS;DIOXIDE