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Photodissociation dynamics of dianions by time-resolved photoelectron spectroscopy
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Image of FIG. 1.
FIG. 1.

Transient intensity and bleach in time-resolved photoelectron spectra of dianions after pump excitation at 1.6 eV and with a probe detachment photon energy of 4.8 eV. Also shown in blue is the probe-only (one-photon) photoelectron spectrum.

Image of FIG. 2.
FIG. 2.

Transient intensity and bleach in time-resolved photoelectron spectra of dianions after excitation at 1.6 eV and detachment with a photon energy of 4.8 eV.

Image of FIG. 3.
FIG. 3.

Suggested dynamics in dianions after excitation at . Decay of the initially excited state proceeds by IC through intermediate state and back to the vibrationally hot electronic ground state . A detailed description of competing dissociative decay pathways is given in the text.

Image of FIG. 4.
FIG. 4.

Integrated electron yield in the binding energy range of 0.00–0.55 eV (upper panel) and 0.55–1.00 eV (lower panel) as a function of pump-probe delay. Circles are experimental data; the lines are least-squares fits, with the thin dashed lines representing contributions from two different excited states.

Image of FIG. 5.
FIG. 5.

Total time-dependent electron yield for the delayed detachment of bromide (upper panel) and binding energies for bromide in the electric field of the remaining fragment for detachment into the ground and excited states of neutral bromine (lower panel). Circles are experimental data points, lines are least-squares fits, as described in the text.

Image of FIG. 6.
FIG. 6.

Potential energy curve along the dissociation coordinate . The equilibrium distance is 2.5 Å and the dissociation barrier is located at 4.13 Å. The zero point vibrational energy amounts to 117 meV. All energetics have been obtained from density functional calculations, restricting symmetry to the point group.

Image of FIG. 7.
FIG. 7.

Unimolecular decay rate for the dissociation over the RCB. Dissociation rates, as well as the corresponding lifetime are given for an internal energy of 2.1 eV and as a function of the RCB height.


Generic image for table
Table I.

Vertical binding energies (in eV) of all features observed in both “ground state” and time-dependent PE spectra of . Capital letters refer to ground state detachment while small letters denote transient detachment features. All labels refer to Fig. 1


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photodissociation dynamics of IrBr62− dianions by time-resolved photoelectron spectroscopy