Femtosecond dynamics of solvated oxygen anions. I. Bifurcated electron transfer dynamics probed by photoelectron spectroscopy

The ultrafast dissociationdynamics of O−_6⋅X (X=O_2, N_2, Xe, or N_2O) was investigated by femtosecondphotoelectron spectroscopy. The transients, monitoring nascent O−_2, exhibit biexponential rises with two distinct time constants—the fast component (τ_1∼200 fs) corresponds to the joint rate constant for electron recombination and direct dissociation of the O−_4 core perturbed by solvent molecules, whereas the slow component (τ_2=2.0–7.7 ps, depending on the solvent) corresponds to the process for the liberation of O−_2, which is governed by vibrational predissociation and intramolecular vibrational-energy redistribution. These observations are consistent with the mechanism proposed in the earlier communication of this work [Paik et al., J. Chem. Phys. 115, 612 (2001)]. The wave packet bifurcates via two separate dissociation pathways: electron transfer followed by electron recombination, and electron transfer followed by vibrational predissociation. Unlike all other solvents, the anomalous behavior observed for O−_6⋅N_2O—a threefold increase in τ_2 value, compared to the other solvents, and a factor of 10 increase for τ_2, compared to that of O−_6—reflects the more effective energy dissipation via solute–solvent vibration-to-vibration and rotational couplings. Moreover, for all solvents, the ratio of the slow-rise contribution to the total signal can be correlated with the degree of cooling, supporting the concept of bifurcation in the two channels