Using the recently developed threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging mass spectrometer (Tang et al. Rev. Sci. Instrum.2009, 80, 113101), dissociation of vibrational state-selected O(2)(+)(B(2)Σ(g)(¯), v(+) = 0-6) ions was investigated. Both the speed and angular distributions of the O(+) fragments dissociated from individually vibronic levels of the B(2)Σ(g)(¯) state were obtained directly from the three-dimensional time-sliced TPEPICO velocity images. Two dissociation channels, O(+)((4)S) + O((3)P) and O(+)((4)S) + O((1)D), were respectively observed, and their branching ratios were found to be heavily dependent on the vibrational states. A new intersection mechanism was suggested for the predissociation of O(2)(+)(B(2)Σ(g)(¯)) ions, especially for dissociation at the energy of the v(+) = 4 level. In addition, the anisotropic parameters for O(+) fragments from different dissociative pathways were determined to be close to zero, indicating that the v(+) = 0-6 levels of B(2)Σ(g)(¯) predissociate on a time scale that is much slower than that of molecular rotation.
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