Excited state dynamics in clusters of oxygen

Li, Runjun; Hanold, K.; Garner, M. C.; Luong, A. Khai; Continetti, Robert E.

doi:10.1039/a705823c

Cited by 24 publications

(48 citation statements)

References 28 publications

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“…A similar situation has been discussed by Li et al for the case of O 4 − ·O 2 dissociation. 4 However, the observations of O 4 − and O 2 − photofragments and the lack of dissociation of clusters without O 2 reported here, as well as the fact that the excitation energy ͑1.55 eV͒ matches the expected energy of a charge-transfer band, 13 i.e., between AEA and VDE of A − ͑O 2 ͒ n , lead us to favor a photoinduced intermolecular electron transfer followed by an ultrafast recombination as a more appropriate reaction mechanism for the absorption of 800 nm light, similar to the mechanism discussed for both neutral and anionic clusters.…”

Section: A Scalar Dynamicsmentioning

confidence: 57%

“…4 However, the observations of O 4 − and O 2 − photofragments and the lack of dissociation of clusters without O 2 reported here, as well as the fact that the excitation energy ͑1.55 eV͒ matches the expected energy of a charge-transfer band, 13 i.e., between AEA and VDE of A − ͑O 2 ͒ n , lead us to favor a photoinduced intermolecular electron transfer followed by an ultrafast recombination as a more appropriate reaction mechanism for the absorption of 800 nm light, similar to the mechanism discussed for both neutral and anionic clusters. 8,9,22 Especially, we have found that oxygen plays a significant role in the photoinduced electron transfer at 800 nm and examined this phenomenon in solvated oxygen anions: For example, we observed that O 4 − X, X = Xe, N 2 , and N 2 O, does not dissociate while O 4 − O 2 dissociates at 800 nm. 9 For A − O 2 , A − rises via two different channels.…”

Section: A Scalar Dynamicsmentioning

confidence: 99%

“…Time-resolved anisotropy has been developed as a reliable method to determine molecular structures and monitor the vectorial dynamics of rotation. [10][11][12] We applied this technique to study the structure and rotational motion of A − ͑O 2 ͒ n clusters and deduced a change in the location of ͑O 2 ͒ n with respect to A − upon going from A − O 2 to A − O 4 . The cluster effect on the rotational motion is examined by measuring the dephasing time of the initial alignment.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7] Rigorous mass selection allows us to follow the evolution of size-dependent properties to bulk and to examine the solvation dynamics as a function of cluster size. In earlier works, we have shown that these aspects appeared in homogeneous and heterogeneous anionic oxygen clusters.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast vectorial and scalar dynamics of ionic clusters: Azobenzene solvated by oxygen

Paik

Baskin

Kim

et al. 2006

The Journal of Chemical Physics

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The ultrafast dynamics of clusters of trans-azobenzene anion ͑A − ͒ solvated by oxygen molecules was investigated using femtosecond time-resolved photoelectron spectroscopy. The time scale for stripping off all oxygen molecules from A − was determined by monitoring in real time the transient of the A − rise, following an 800 nm excitation of A − ͑O 2 ͒ n , where n =1-4. A careful analysis of the time-dependent photoelectron spectra strongly suggests that for n Ͼ 1 a quasi-O 4 core is formed and that the dissociation occurs by a bond cleavage between A − and conglomerated ͑O 2 ͒ n rather than a stepwise evaporation of O 2 . With time and energy resolutions, we were able to capture the photoelectron signatures of transient species which instantaneously rise ͑Ͻ100 fs͒ then decay. The transient species are assigned as charge-transfer complexes: A ·O 2 − for A − O 2 and A ·O 4 − · ͑O 2 ͒ n−2 for A − ͑O 2 ͒ n , where n =2-4. Subsequent to an ultrafast electron recombination, A − rises with two distinct time scales: a subpicosecond component reflecting a direct bond rupture of the A − -͑O 2 ͒ n nuclear coordinate and a slower component ͑1.6-36 ps, increasing with n͒ attributed to an indirect channel exhibiting a quasistatistical behavior. The photodetachment transients exhibit a change in the transition dipole direction as a function of time delay. Rotational dephasing occurs on a time scale of 2 -3 ps, with a change in the sign of the transient anisotropy between A − O 2 and the larger clusters. This behavior is a key indicator of an evolving cluster structure and is successfully modeled by calculations based on the structures and inertial motion of the parent clusters.

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Section: A Scalar Dynamicsmentioning

confidence: 57%

Section: A Scalar Dynamicsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ultrafast vectorial and scalar dynamics of ionic clusters: Azobenzene solvated by oxygen

Paik

Baskin

Kim

et al. 2006

The Journal of Chemical Physics

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“…These microscopic solvation processes, which may involve energy redistribution, electron transfer, and vibrational predissociation, have been examined in a variety of ionic [1][2][3][4][5][6][7][8][9] and neutral [10][11][12][13][14] clusters.…”

Section: Introductionmentioning

confidence: 99%

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

Paik

Kim

Zewail

2003

The Journal of Chemical Physics

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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.

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Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

Павлов

2013

Surv Geophys

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Excited state dynamics in clusters of oxygen

Cited by 24 publications

References 28 publications

Ultrafast vectorial and scalar dynamics of ionic clusters: Azobenzene solvated by oxygen

Ultrafast vectorial and scalar dynamics of ionic clusters: Azobenzene solvated by oxygen

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

Photochemistry of Ions at D-region Altitudes of the Ionosphere: A Review

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