Potential energy curves for the relevant electronic states of (a) , (b) IBr and the corresponding anions: (c) and (d) . The potential curves corresponding to the neutral states of and IBr are obtained from Refs. 30, 31, 68, 69, 73, 74, 78, 79, and 79–81, respectively. The potentials are from the scaled calculations in Refs. 58 and 59, with the exception of the and states, which are experimentally determined in Refs. 3, 4, 10, and 57. The curves are from Refs. 37 and 38. The vertical arrows in (c) and (d) represent the pump transition accessing the states of the respective anions. The dashed curves in (a) and (b) represent the anion potentials projected on the respective neutral manifolds by the addition of the probe photon energy. Further details are given in the text.
Representative time-resolved raw photoelectron images recorded at selected pump–probe delays in the 780 nm pump–390 nm probe experiments on (left) and (right). The pump and probe polarization directions are vertical in the plane. The images are shown on arbitrary relative intensity scales.
(Color) Time-resolved photoelectron spectra obtained in the dissociation of (a) and (b) using a 780 nm pump, while detaching the electrons with 390 nm probe pulses. The spectra are obtained from photoelectron images, a selection of which is shown in Fig. 2.
(Color) Time–energy contour plots of the time-resolved photoelectron spectra shown in Fig. 3 in the range of 50–750 fs and 0.0–0.3 eV for (a) and (b) . In (a), the dashed white curves represent trajectory simulations with detachment via the labeled neutral states. The solid black line represents a mean of the individual detachment channels, calculated as described in the text. In (b), the lines represent trajectories corresponding to the different values of indicated. The “best fit” (as determined by inspection), corresponding to , is indicated by the solid black line.
(Color) An image of the potential based on the experimental data and semiclassical model described in the text. The corresponding theoretical potential energy curve (Refs. 37 and 38) is shown for comparison as a white line.
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