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• W2002646128 abstract "The ultrafast dissociation dynamics of O6−⋅X (X=O2, N2, Xe, or N2O) was investigated by femtosecond photoelectron spectroscopy. The transients, monitoring nascent O2−, exhibit biexponential rises with two distinct time constants—the fast component (τ1∼200 fs) corresponds to the joint rate constant for electron recombination and direct dissociation of the O4− core perturbed by solvent molecules, whereas the slow component (τ2=2.0–7.7 ps, depending on the solvent) corresponds to the process for the liberation of O2−, 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 O6−⋅N2O—a threefold increase in τ2 value, compared to the other solvents, and a factor of 10 increase for τ2, compared to that of O6−—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." @default.
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• W2002646128 date "2003-03-31" @default.
• W2002646128 modified "2023-10-16" @default.
• W2002646128 title "Femtosecond dynamics of solvated oxygen anions. I. Bifurcated electron transfer dynamics probed by photoelectron spectroscopy" @default.
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• W2002646128 doi "https://doi.org/10.1063/1.1561433" @default.
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