Dynamic molecular interferometer: Probe of inversion symmetry in I ₂ ^- photodissociation

Time-resolved photoelectron imaging of negative ions is employed to examine 780-nm dissociation dynamics of I2-, emphasizing the effects of interference in time-resolved photoelectron angular distributions obtained with 390-nm probe. No energetic changes are observed after about 700 fs, but the evolution of the photoelectron anisotropy persists for up to 2.5 ps, indicating that the electronic wave function of the dissociating anion continues to evolve long after the asymptotic energetic limit of the reaction has been effectively reached. The time scale of the anisotropy variation corresponds to a fragment separation of the same order of magnitude as the de Broglie wavelength of the emitted electrons (λ=35 Å). These findings are interpreted by considering the effect of I2- inversion symmetry and viewing the dissociating anion as a dynamic molecular-scale "interferometer," with the electron waves emitted from two separating centers. The predictions of the model are in agreement with the present experiment and shed new light on previously published results [A. V. Davis, R. Wester, A. E. Bragg, and D. M. Neumark, J. Chem. Phys. 118, 999 (2003)].