The evolution of the I- channel in I2Br- photodissociation is examined using time-resolved negative-ion photoelectron imaging spectroscopy. The 388 nm photodetachment images obtained at variable delays following 388 nm excitation reveal the transformation of the excess electron from that belonging to an excited trihalide anion to that occupying an atomic orbital localized on the I- fragment. With increasing pump-probe delay, the corresponding photoelectron band narrows on a similar to300 fs time scale. This trend is attributed to the localization of the excess-electron wave function on the atomic-anion fragment and the establishment of the fragment's electronic identity. The corresponding band position drifts towards larger electron kinetic energies on a significantly longer, similar to1 ps, time scale. The gradual spectral shift is attributed to exit-channel interactions affecting the photodetachment energetics, as well as the photoelectron anisotropy. The time-resolved angular distributions are analyzed and found consistent with the formation of the asymptotic I- fragment. (C) 2004 American Institute of Physics.