Vibrational coherence in ultrafast electron-transfer dynamics of oxazine 1 in N,N-dimethylaniline: simulation of a femtosecond pump-probe experiment

Wolfseder, Brigitte; Seidner, Luis; Domcke, Wolfgang; Stock, Gerhard; Seel, M.; Engleitner, S.

doi:10.1016/s0301-0104(98)00132-3

Cited by 66 publications

(54 citation statements)

References 38 publications

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“…The MCWP technique was first introduced for dissipative processes in quantum optics [14][15][16] and was later used successfully in numerous studies [16][17][18][19][20][21] and also in molecular physics [22,23]. In the IR regime the method was applied to the problem of strong-field dissociative ionization of H 2 and D 2 , and allowed an identification of the different structures in the KER spectra in terms of physical mechanisms such as three-photon resonances and charge-resonance-enhanced ionization in the cation [24][25][26].…”

Section: Dissociative Multiple Ionization In the Euv Using The Momentioning

confidence: 99%

Dissociative multiple ionization of diatomic molecules by extreme-ultraviolet free-electron-laser pulses

Leth

Madsen

2011

Phys. Rev. A

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Nuclear dynamics in dissociative multiple ionization processes of diatomic molecules exposed to extremeultraviolet free-electron-laser pulses is studied theoretically using the Monte Carlo wave packet approach. By simulated detection of the emitted electrons, the model reduces a full propagation of the system to propagations of the nuclear wave packet in one specific electronic charge state at a time. Suggested ionization channels can be examined, and kinetic energy release spectra for the nuclei can be calculated and compared with experiments. Double ionization of O 2 is studied as an example, and good agreement with published experimental data is obtained by simulating the dynamics on ten different electronic Born-Oppenheimer curves.

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Section: Dissociative Multiple Ionization In the Euv Using The Momentioning

confidence: 99%

Dissociative multiple ionization of diatomic molecules by extreme-ultraviolet free-electron-laser pulses

Leth

Madsen

2011

Phys. Rev. A

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“…Intermolecular electron transfer can take place in hundreds of femtoseconds when one of the redox partners is present at high concentration, eliminating the need for diffusion. 32,[71][72][73][74] In acetonitrile, where the solvent itself acts as the electron acceptor, it is unnecessary for the electron and an acetonitrile molecule to diffusively encounter one another, and ultrafast reaction must be considered. In fact, Jortner et al argued in the early 1960s that reaction of the excess electron with the solvent is extremely slow in acetonitrile.…”

Section: Rate Of Solvent Anion Formationmentioning

confidence: 99%

Femtosecond electron ejection in liquid acetonitrile: Evidence for cavity electrons and solvent anions

Xia

Peón

Kohler

2002

The Journal of Chemical Physics

138

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Articles you may be interested inPhotodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide J. Chem. Phys. 137, 034512 (2012); 10.1063/1.4736569Collisional electron transfer to photoexcited acceptor radical anions Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopyExcess electrons were studied in liquid acetonitrile at room temperature by femtosecond pumpprobe spectroscopy. Using Ϸ200 fs, 265 nm laser pulses, electrons were ejected into the liquid by photodetachment from iodide ions and, in separate experiments, by photoionization of indole. A strong and broad absorption band with a maximum near 1400 nm was observed in both systems. A second absorption band was observed at wavelengths below 620 nm for iodide solutions, but was not seen in photoexcited indole due to overlapping excited state absorption. The bands are in good agreement with ones seen previously in nanosecond pulse radiolysis experiments ͓I. P. Bell, M. A. J. Rodgers, and H. D. Burrows, J. Chem. Soc., Faraday Trans. 1 73, 315 ͑1977͔͒. Bell, Rodgers, and Burrows assigned the visible and IR bands to absorption by acetonitrile dimer and monomer anions, respectively. Our results strongly question this interpretation. Instead, we assign the short-wavelength absorption band to a solvent-bound valence anion consisting of one or two acetonitrile molecules and the IR band to a solvated or cavity electron. Low-level quantum chemical calculations indicate that valence anion formation is strongly correlated with CCN bending, but do not provide a clear indication of whether a monomer or dimer valence anion is favored. The highly mobile cavity electron is scavenged by added chloroform at a bimolecular reaction rate of (1.02 Ϯ0.03)ϫ10 11 M Ϫ1 s Ϫ1 . The appearance of both absorption bands within our time resolution suggests that the two forms of the excess electron are produced by prompt reaction with the iodide charge-transfer-to-solvent ͑CTTS͒ excited state. In support of this mechanism, strong static scavenging by chloroform was observed at both visible and IR wavelengths. For iodide in acetonitrile, the signal in the IR decays biexponentially due to competition between geminate recombination of the cavity electron with the parent iodine atom and its reaction with the solvent. Geminate recombination between the solvated electron and the parent iodine atom occurs with a characteristic time constant of Ϸ30 ps, while additional solvent anions are formed in a slow reaction with a time constant of Ϸ260 ps. Approximately 30% of the solvated electrons photodetached from iodide undergo geminate recombination. There is no evidence for geminate reaction between the promptly formed solvent anion and iodine, suggesting that these species are formed at larger initial separation than the IR-absorbing cavity electron/iodine atom pair. In indole, geminate recombination occurs on a slower time scale of Ϸ135 ps.

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“…Employing femtosecond nonlinear spectroscopy techniques, it has been demonstrated that in these ET reactions the coupling to both intramolecular modes of the donor-acceptor complex as well as to the solvation dynamics can have significant effects on the ET dynamics. 2,4 -8 Moreover, the observation of oscillatory features in time-resolved spectroscopic signals for several ET reactions 5,6,[9][10][11][12] has raised intriguing questions about the occurrence and observability of electronic and vibrational quantum coherence in a condensed phase environment.…”

Section: Introductionmentioning

confidence: 99%

Modeling of ultrafast electron-transfer processes: Validity of multilevel Redfield theory

Egorova

Thoss

Domcke

et al. 2003

The Journal of Chemical Physics

162

112

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Articles you may be interested inThree-centered model of ultrafast photoinduced charge transfer: Continuum dielectric approach A perturbation molecular orbital theory of electron-transfer ratesThe capability of multilevel Redfield theory to describe ultrafast photoinduced electron-transfer reactions is investigated. Adopting a standard model of photoinduced electron transfer in a condensed-phase environment, we consider electron-transfer reactions in the normal and inverted regimes, as well as for different values of the electron-transfer parameters, such as reorganization energy, electronic coupling, and temperature. Based on the comparison with numerically exact reference results, obtained using the self-consistent hybrid method, we discuss in some detail the advantages and shortcomings of two different versions of Redfield theory, which employ the time-dependent and stationary Redfield tensor, respectively. The results of the study demonstrate that multilevel Redfield theory, if applied in the appropriate parameter regime, is well suited to describe the ultrafast coherent dynamics of photoinduced electron-transfer reactions.

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Vibrational coherence in ultrafast electron-transfer dynamics of oxazine 1 in N,N-dimethylaniline: simulation of a femtosecond pump-probe experiment

Cited by 66 publications

References 38 publications

Dissociative multiple ionization of diatomic molecules by extreme-ultraviolet free-electron-laser pulses

Dissociative multiple ionization of diatomic molecules by extreme-ultraviolet free-electron-laser pulses

Femtosecond electron ejection in liquid acetonitrile: Evidence for cavity electrons and solvent anions

Modeling of ultrafast electron-transfer processes: Validity of multilevel Redfield theory

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